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CHRISTIANSEN, JRGENSEN, AND HATTIG
1. Introduction
CHRISTIANSEN, JRGENSEN, AND HATTIG
efficient calculation of excited-state gradients and
vibrational frequencies. Excited-state gradients for
coupled-cluster theory have previously been derived in other contexts w 34]36x . The Lagrangian for
an excited state is another example of the strength
of the variational Lagrangian technique. Here, a
new carrier functional is defined by incorporating
the appropriate constraints multiplied by Lagrangian multipliers and the usual Lagrangian
machinery then assures that the 2 n q 1 and 2 n q 2
rules are obeyed. The definition of intermediates
in terms of partial derivatives of a quasienergy
Lagrangian combined with the 2 n q 1 and 2 n q 2
rules also provides the means for a flexible and
computational efficient implementation.
In Section 2 we discuss general aspects of the
response theory and describe the basic theory,
allowing the determination of response functions
using Fourier component variational perturbation
theory. In Section 3, we discuss the derivation of
response function in an explicit but yet not specified parametrization, and in Section 4, we apply
the results to the derivation of response functions
for exact and SCF response functions. In Section 5,
we discuss the derivation of CC response functions
as well as give a brief discussion on the evaluation
of MP2 dynamic properties. In Section 6, the evaluation of molecular properties from response theory is discussed. Finally, section 7 contains some
concluding remarks.
Vts
exp yi v k t . V v k
ksyN
N
exp yi v k t . x v k . X .
2.4.
X s X,
vyk s yv k ,
2.5.
2.6.
xU v k . s x vyk . .
2.7.
This is fulfilled if
and
x v k . s xR v k . q i xI v k . .
Vts
expyi v k t . q expqi v k t ..
ks1
= xR v k . X
x
N
<0: ,
expyi v k t . y expqi v k t ..
qi
2.1.
ks1
= xI v k . X
where
H s H0 q V .
t
2.2.
x 0. X
x
2.8.
H <0: s i
2.3.
ksyN
x 0. X q 2 cos v k t . xR v k . X
x
ks1
q2
sin v k t . xI v k . X ,
ks1
2.9.
V t
s X exp yi v k t . .
x v k .
2.10.
The sum over frequencies contains all the considered physical fields. However, we may also choose
to include in the sum fields that are not among the
applied physical perturbations, but are introduced
with the sole purpose to simplify the identification
of the response functions. It is legitimate to include
these fields because the application of these fields
is controlled by the strength parameters. The importance of introducing such fields will be clear
later.
We may write the wave function in the phase
isolated form as
<0: s eyi F t . <
0: ,
eyi F t . H y i
y F t . <
0: s 0,
2.12.
Hyi
y F t . <
0: s 0.
2.13.
Projection onto
0 < determines F t . as
F t . s
0 Hyi
/ ;
0 .
2.14.
H0 <0: s E0 <0: ,
2.15.
0 <0: s 1.
2.16.
response functions may be determined by expanding the average value of X in orders of the perturbation
X : t . s 0 < X <0: s
0 < X <
0:
s X :0 q
expyi v k t .
1
k1
= X ; Y :: v k y v k 1 .
1
1
2
k1 , k 2
exp yi v k 1 q v k 2 . t .
= X ; Y , Z :: v k
y, z
q ???
2.11.
, v k2 y vk
. z vk .
2
2.17.
We assume that X does not contain differentiation with respect to time and the reference to F
therefore cancels in the expectation value. The
linear response function, X; Y ::v k 1, the quadratic response function, X; Y, Z ::v k 1 , v k 2 , and
so on are the expansion coefficients of the Fourier
components. For time-independent perturbations
where the frequency parameters of the perturbations are zero, Eq. 2.17. reduces to an ordinary
CHRISTIANSEN, JRGENSEN, AND HATTIG
Taylor expansion of the static expectation value of
X where the response functions X; Y :: 0 ,
X; Y, Z :: 0, 0 ??? are the expansion coefficients.
The complex conjugated of the expectation value
in Eq. 2.17. becomes using Eqs. 2.6. and 2.7.
X :* t .
U
s X :0 q
expqi v k t .
1
k1
U
= X ; Y :: v k Uy v k 1 .
1
1
2
k1 , k 2
exp qi v k 1 q v k 2 . t .
U
= X ; Y , Z :: v k
U
, v k2 y vk
y, z
q ???
U
s X :0 q
. zU v k .
expyi v k 1 t .
k1
= X ; Y :: yv k y v k 1 .
F t . s E0 ,
1
2
k1 , k 2
exp yi v k 1 q v k 2 . t .
U
= X ; Y , Z :: yv k
, yv k 2 y v k
y, z
. z vk .
q ???
2.18.
X :0 s
X ; Y :: v k s X ;
1
X ; Y , Z :: v k
, v k2
s X ; Y , Z :: y v k
X ; Y , Z, ??? :: v k
, yv k 2
, y v k 2 , ??? .
2.22.
s
0 Hyi
2.21.
0
t
d
0 <
0:
s
0 < H <
0: q i
2.20.
, v k 2 , ???
s X ; Y , Z, ??? :: yv k
F t . * s H
0 <
0: q y i
2.19.
U
Y :: y v k 1
2.24.
2.23.
dt
;
;
y
0
/ ;
0 s F t . ,
2.25.
0 <0: s
d
dt
0 <
0: s
; ;
t
0 q 0
s 0.
2.26.
Since F t . reduces to E0 in the time-independent limit w Eq. 2.23.x , we denote this quantity,
Q t . s F t . s
0 Hyi
/ ;
0 ,
Hyi
y Q <
0: s 0.
d0 H y i
/;
yQ
0 s 0.
2.30.
Since < d
0: and d F are independent variations, we
obtain by inserting Eq. 2.30. into Eq. 2.29.
Frenkels time-dependent variational principle w 24x :
d
0 Hyi
/;
yQ
0 s 0.
2.34.
where < d
0 H : is orthogonal to <
0:, and d a is real
according to Eq. 2.33.. From the definition of Q in
Eq. 2.27., we see that in Eq. 2.31. the contribution
from variations along <
0: vanish and we may thus
write Eqs. 2.31. and 2.33. in the equivalent forms:
d 0H H y i
0 s 0
2.35.
and
d
0 H <
0: s 0.
2.36.
These equations are equivalent to those of Moccia w 28x . If all variational parameters have independent real and imaginary orthogonal variations, we
thus have an equation similar to Eq. 2.35. with the
variation i d
0 H <. These equations are equivalent
to the symmetrized form of Frenkels variation
principle:
Re d
0 Hyi
0 s 0,
2.37.
where d
0 H < may be substituted by i d
0 H <. Using
that i a
0 < H y i r t .<
0: is purely imaginary, we
can reintroduce <
0: and write Eq. 2.37. as
Re d
0 Hyi
/ ;
0 s 0,
2.38.
d
0 Hyi
/ ;
0 q
Hyi
/ ;
0 d 0 s 0,
2.39.
2.31.
<d
0: s < d
0 H : q i d a <
0: ,
2.29.
2.33.
2.28.
d
0 <
0: q
0<d
0: s 0.
2.27.
the time-dependent quasienergy. The time-dependent quasienergy is what Langhoff et al. denoted
level-shift w 21x and other names have been proposed w 31x . Q t . was denoted quasienergy by
Sasagane et al. w 7x , however, we reserve the term
quasienergy for the time-average of Q t . in agreement with earlier work w 33x . We shall see later that
it is the time-averaged quasi-energy that in the
deviation of response functions takes the role closest to the one of the energy in usual time-independent theory. The time-dependent quasienergy can
be obtained from Eq. 2.27. once we have determined <
0:. We shall therefore concentrate on the
determination of the <
0: wave function in the remainder of this subsection. The time-dependent
Schrodinger
equation in the phase-isolated form
an allowed variation of d
0 < must fulfill that
2.32.
d
0 Hyi
/ ;
0 qi
0<d
0: s 0. 2.40.
CHRISTIANSEN, JRGENSEN, AND HATTIG
In the time-independent limit, Eq. 2.35. corresponds to
d
0 < H <
0: s 0,
2.41.
d
0 < H <
0: s 0.
2.42.
In the time-independent limit, Eq. 2.40. thus corresponds to the usual variational criterion, while
Eq. 2.35. corresponds to projected equations which
may or may not be equivalent.
The above Eqs. 2.35., 2.38., and 2.40. for the
time evolution are completely general and determine the same solution to the time-dependent
Schrodinger
equation for a sufficiently flexible trial
d Q t . q i
0<d
0: s 0.
2.43.
d
0 < H <
0:
d
s
0
0 ,
2.44.
dQ
d
d
0 Hyi
s
/ ;
0
s
0
; ;
0 y i
d0
d
2.45.
H
s X exp yi v t . ,
x v .
2.46.
0 < X <
0:exp yi v t . s
dQ t .
dx v .
qi
d0
d x v .
2.47.
The fundamental difference between time-dependent theory and time-independent theory is seen
comparing the time-dependent equations w Eqs.
2.43. and 2.45.x and the time-independent ones
w Eqs. 2.42. and 2.44.x . In the time-dependent
equations, the time-dependent quasienergy Q has
replaced the ordinary energy E. However, the
2.48.
Tr2
H f t . dt.
T yTr2
2.49.
Z t .
d Q t .4 T s 0,
d Q t .4 T
d x v .
2.50.
s 0.
2.52.
d
0 H0 y i
/;
0 q i
0<d
0: s yd
0 < V <
0: .
2.53.
<0 1. v k .:expyi v k t . .
1
k1
2.54.
<0 2. v k , v k
1
k1 , k 2
.:
= exp yi v k 1 q v k 2 . t .
<
0 m. t .: s
s
0 < X <
0:exp yi v t . 4 T . 2.51.
k 1 , k 2 ??? k m
2.55.
<
0 m. v k 1 , v k 2 , ??? v k m .:
m
= exp yi
vk t
ns1
2.56.
CHRISTIANSEN, JRGENSEN, AND HATTIG
Thus, the mth-order wave-function response <
0:
is a product of factors oscillating with frequencies
corresponding to the form of the perturbation in
Eq. 2.3.. Since it is built from products of functions with the periodicity in Eq. 2.48., the mthorder response will also be periodic with period T.
Note that <
0: and not <0: has this periodic behavior. Since <
0: is periodic to all orders in V with a
similar periodicity as V, it may be expanded in
terms of Fourier components similar to the perturbation in Eq. 2.3.. We may further separate the
contributions from the time-dependent variational
principle in Eq. 2.43. into a zero-phase part and an
oscillating part. The zero-phase part is the timeaveraged form in Eq. 2.50.. The remainder vanish
when we take the time average. This remainder is
not necessary for determining the time evolution
of <
0:. An order-by-order expansion of the zerophase part will include to higher and higher order
all the Fourier components of the perturbed wave
function and is sufficient to uniquely determine
these Fourier components. Since we showed
above that <
0: has the oscillatory form in Eqs.
2.54. ] 2.56., we thus have that the time-averaged
time-dependent variational condition is sufficient
to determine the correct time evolution of <
0: in
the case of periodic perturbations. The time-dependent quasienergy can then be obtained from Eq.
2.27. and we have the complete solution to our
problem.
Response functions are conveniently identified
from Eq. 2.51. as we will now demonstrate. At
this stage, it is appropriate to return to the discussion of the form of the perturbation in Eq. 2.3.. As
stated previously, we may include in the expansion perturbations that are convenient for the
derivation of response functions. We therefore also
include the field X with frequency v 0 corresponding to the sum of a number of frequencies for the
perturbations in Eq. 2.3.. In this way, X may be
treated with a similar basis at the other perturbations. Inserting expansion Eq. 2.17. that defines
the response functions into Eq.2.51. gives
d Q t .4 T
d x v .
s X: q
X ; Y ::v
y
k1
k1
= y v k 1 . d v q v k 1 .
q
10
1
2
y, z k 1 , k 2
X ; Y , Z ::v k
= y v k 1 . z v k 2 . d v q v k 1 q v k 2 .
q ??? ,
2.57.
d Q4 T
d x 0.
d 2 Q4 T
d x v 0 . d y v k1 .
2.58.
;
v 0 s yv k 1 ,
X ; Y , Z ::v k
, v k2 s
1
2.59.
d 3 Q4 T
d x v 0 . d y v k1 . dz v k 2 .
v 0 s yv k 1 y v k 2 ,
X ; Y , Z, ??? ::v k
s
2.60.
, v k2 , . . .
d nq 1 Q 4 T
d x v 0 . d y v k 1 . d z v k 2 . ???
v0 s y vki .
2.61.
is1
v0 s y vki ,
1
, v k2
2.62.
is1
, v k2
U
vk3
q
q
2.64.
???
???
X : x 0.
x
1
2
X ; Y ::v
x , y k1
k1
2.65.
X :* x 0.
x
x yv k 1 . y v k 1 .
1
2
X ; Y ::yv
x , y k1
1
6
k1
x y v k 1 . y v k 1 .
X ; Y , Z ::Uyv k
xyz k 1 , k 2
, v k2
= x yv k 1 y v k 2 . y v k 1 . z v k 2 .
In general, permutational symmetry exists between the operators and associated frequencies:
Z
vk2
, v k2
s Y , X , Z ::yv k 1y v k 2 , v k 2
Y
v k1
q ??? .
s Z, Y , X ::v k 1 , y v k 1y v k 2
X
v0
X ; Y , Z ::v k
x , y , z k1, k 2
= x yv k 1 y v k 2 . y v k 1 . z v k 2 .
s X , Z, Y ::v k 2 , v k 1
Operator:
Frequency:
Q* 4 T s Q 4UT s E0 q
s Z, X , Y ::yv k 1y v k 2 , v k 1
s Y , Z, X ::v k 2 , y v k 1y v k 2 .
2.63.
Similar symmetry relations hold for the higherorder response functions as a consequence of
identifying the response functions by the differentiations in Eqs. 2.59. ] 2.61.. For the quadratic
response function,
X , Y , Z ::v k
q ???
s Q4 T .
2.66.
0 1 H y i
Q t . s
/ ;
02
0 1 <
02 :
2.67.
Im w Q t .x s y
1
2 t
ln0 <0 : / .
1
2.68.
11
CHRISTIANSEN, JRGENSEN, AND HATTIG
Thus, even if the wave function is not normalized
as was assumed in deriving Eq. 2.25., the
quasienergy is real:
Q t .4 T s Re w Q t .x 4 T .
2.69.
In variational theories, 0 1 s 0 2 and the quasienergy is real. The symmetry relations in Eqs.
2.19. ] 2.22. are therefore fulfilled. For some nonvariational methods not all., 0 1 / 0 2 and we are
not ensured that the quasienergy is real. This problem is not confined to time-dependent theory. For
example, if we have complex functions in a timeindependent theory, for example, due to magnetic
perturbations, then the energy evaluated from Eq.
2.67. is not real even in the static limit. In time-dependent theory, this asymmetry, 0 1 / 0 2 , has, as a
consequence, that the quasienergy is not necessarily real and that the fundamental symmetry relations in Eqs. 2.19. ] 2.22. are not fulfilled. Since
the symmetry relations are necessary to have a real
expansion of the expectation value of a Hermitian
operator, they are crucial for a meaningful identification of physical properties. See also the discussion in Section 6.. We must therefore enforce these
symmetry relations explicitly if they are not
straightforwardly satisfied. This can be done in
several ways: One way is simply to ignore this
artifact in the derivation of response functions and
identify the response functions as derivatives of
the quasienergy as indicated up to this point. The
expansion in Eq. 2.17. may then have a complex
part while only the real part has a physical significance. Accordingly, the true response properties
may be determined from the symmetrizations,
X :0
X ; Y ::v k
1
1
2
X : 0 q X :U0 . ,
X ; Y ::v
2
k1
2.70.
U
q X ; Y ::y v k 1 . ,
2.71.
X ; Y , Z ::v k
, v k2
1
2
X ; Y , Z ::v
k1 ,
v k2
U
q X ; Y , Z ::yv k 1 , y v k 2 . ,
X ; Y , Z, ??? ::v k
1
2
k1 ,
v k 2 ???
U
q X ; Y , Z ::yv k 1 , y v k 2 , ??? . ,
12
2.72.
, v k2
X ; Y , Z, ??? ::v
2.73.
1
2
E q E* . .
2.74.
d Re Q t .4 T s 0
d Re Q t .4 T
d x v .
2.75.
s X : t . exp yi v t .4 T . 2.76.
X : x 0.
Q 4 T s E0 q
q
q
1
2
X , Y ::0 x 0. y 0.
x, y
1
6
X , Y , Z :: 0, 0 x 0 . y 0 . z 0 .
x, y, z
q ???
2.77.
2.78.
d2E .
d x 0. d y 0.
d2E .
d y 0. d x 0.
The symmetries of the frequency-independent response function correspond to simple permutations of operators X, Y, Z, etc., and are special
cases of the symmetry relations for frequency-dependent response functions, where the symmetries
are generalized to permutations of operators and
associated frequencies: X, v 0 ., Y, v k 1 ., Z, v k 2 .,
etc. If only the operators are interchanged, a different frequency-dependent property is obtained. For
example,
1
, v k2
2.79.
X ; Y , Z ::v k
/ X ; Z, Y ::v k 1 , v k 2 , 2.80.
We denote the parameters in our model commonly as l and we assume that the time-depen.. and the time-dependent quasienergy Q l, l
, l . s Q l , l. q l e l , l. ,
L l, l
3.1.
where l are time-dependent Lagrangian multipliers. Variational wave functions are treated as the
special case where l s 0. A comment on the notation is in place. Throughout the remainder of this
article, we use normal types for vectors, while
bold face is preserved for matrices and supermatrices. We use a supermatrix notation where vectors
and matrices are multiplied in orderthus, lB l1l2
denotes the scalar i jk l i Bi jk l1j l2k . We use bars to
denote multiplier vectors. In accord with the discussion in the preceding sections, we proceed to
the time-averaged formalism and derive the response functions using Fourier component varia-
13
CHRISTIANSEN, JRGENSEN, AND HATTIG
tional perturbation theory. The parameters are expanded in orders of the periodic perturbation,
3.2.
3.3.
l1. t . s
k 1syN
l2. t . s
k 1 , k 2syN
exp yi v k 1 q v k 2 . t .
=l2. v k 1 , v k 2 . ,
3.5.
l1. v k 1 . s
l2. v k 1 , v k 2 . s
1
2
x vk . lX vk . ,
1
X vk . Y vk
1
x, y
3.6.
=l X Y v k 1 , v k 2 . .
3.7.
Similar expressions are introduced for the multipliers. Instead of the Fourier decomposition in
Eqs. 3.2. ] 3.5., we may alternatively write the l
parameters as a sum over possible frequency
combinations:
l t . s
expyi v I t . l v I . ,
In variational perturbation theory for a timeindependent perturbation, the change of variables from field-dependent variables l . to the
variables in each order of the perturbation
l1., l2., l3. ??? , is carried out in one step. In
Fourier component variational perturbation theory, the corresponding change of variables is carried out in two steps: First, the introduction of the
time average implies a shift from the time-dependent variables and their derivatives with respect to
t, ., to the Fourier components
time, l t, ., l
1.
2.
l v 1 , ., l v 1 , v 2 , . ??? w or the set of l v I , .
parametersx . These parameters depend on the field
strengths, here explicitly written out as a functional dependency of , and are the analogs
to l . in time-independent theory. Second, we
introduce the parameter responses l Y v 1 .,
lY Z v 1 , v 2 ., ??? to the specific perturbations. These
parameters do not depend on the field strengths as
they are defined as derivatives taken for zero-field
strengths. They are, thus, the analogs to the
l1., l2., l3. parameters of time-independent theory.
We now proceed to derive the response functions from Fourier component variational perturbation theory by carrying out an expansion of the
quasienergy Lagrangian similar to the one just
described for the parameters
L t . s L0. q L1. t . q L2. t . q L3. t .
q L4. t . q ???
3.8.
L0. 4 T s L0. 0 . ,
where
k 1syN
l1. v k 1 . d v k 1 y v I .
N
k 1 , k 2syN
L2. 4 T s
1
2
X v 0 . Y v k . LX Y v 0 , v k . ;
1
k1 x , y
l2. v k 1 , v k 2 .
=d v k 1 q v k 2 y v I . q ???
v 0 s yv k 1 ,
3.9.
14
3.12.
3.11.
x 0. LX 0. ,
L1. 4 T s
l v I . s
3.10.
L3. 4 T s
1
6
k1, k 2 x , y , z
3.13.
X v 0 . Y v k1 . Z v k 2 .
=LX Y Z v 0 , v k 1 , v k 2 . ;
v 0 s y v k1 q v k 2 . ,
3.14.
1
24
k1, k 2 , k 3 x , y , z , u
X v 0 . Y v k1 .
= Z v k 2 . U v k3 .
= LX Y ZU v 0 , v k 1 , v k 2 , v k 3 . ;
v 0 s y v k1 q v k 2 q v k 3 . .
3.15.
3.B. THE ZEROTH-ORDER LANGRANGIAN
n.
Note that the L t ., in general, contain a summation over n frequencies and that this sum is
reduced to a sum over n y 1 frequencies when
the time averaging is carried out. The parameter
responses are determined from the variational
criterion
d L4 T s 0,
3.16.
which in the Fourier component variational perturbation theory becomes variational criteria
for the Fourier components of the quasienergy
Lagrangians L0., LX 0., LX Y v 0 , v k 1 ., LX Y Z v 0 ,
v k 1, v k 2 ., and LX Y ZU v 0 , v k 1, v k 2 , v k 3 . with respect
to variations in the parameter and multiplier responses. When the variational equations have been
solved, the Fourier components of the quasienergy
Lagrangian become equal to the response functions as is clear from Eqs. 2.57. ] 2.61.. The response functions are thus determined as derivatives of L n.4T with respect to the field-strength
variables y v Y .; for example, the linear response
functions become
X ; Y ::v k s
1
d 2 L2. 4 T
d x v 0 . d y v k1 .
v 0 s yv k 1 .
3.17.
s e 0. l0. . .
3.19.
0s
E 0. l0. .
l0.
q l0.
e 0. l0. .
.
l0.
3.20.
The unperturbed reference parameters l0. are required to calculate the energy and all other properties. The zeroth-order multipliers are required to
calculate all ground-state properties except the energy. We do not need to calculate the unperturbed
energy from Eq. 3.18., but may calculate it from
E 0. l0. .. The use of the variational functional is a
great advantage for all properties except the
ground-state energy. The zeroth-order multipliers
in the Lagrangian formalism are the analog of the
so-called Z-vector in the interchange technique for
calculation of analytical first derivatives of nonvariational energies w 19, 20x . In the Lagrangian approach, the Z-vector arises automatically without
resorting to the interchange technique.
Variational theory becomes the special case of
the nonvariational theory where the second term
in Eq. 3.20. vanishes. We obtain the standard
variational criterion for the unperturbed parame-
15
CHRISTIANSEN, JRGENSEN, AND HATTIG
ters l0. :
E 0. l0. .
l0.
X: s
3.21.
Q 1. 4 T
e 1. 4 T
q l0.
.
X 0 .
X 0 .
3.26.
Q 1. 4 T
.
X 0 .
3.27.
d L1. 4 T
d X 0.
L1. 4 T
L1. 4 T X
q 1.
l 0.
X 0 .
l 0 .
q l X 0.
L
1. 4
1.
0.
The variational criterion for the first-order multipliers gives an equation for the reference amplitudes, since
0s
0.
l X 0 .
L1. 4 T
l1. 0 .
3.23.
This equation is, in fact, identical to the one obtained from 0 s w L0.4T x rw l0. x in Eq. 3.19. as
we will see later. The variational criterion for the
first-order parameters gives
0s
LX 0.
L1. 4 T
s
,
l X 0 .
l1. 0 .
3.24.
L1. 4 T
.
X 0 .
3.25.
This is the generalized Hellmann]Feynman theorem stating that all first-order properties including
molecular gradients can be calculated from the
16
d 2 L2. 4 T
d X v 0 . d Y v k1 .
s P X v 0 . , Y v k1 . .
q
2 L2. 4 T
2 X v 0 . Y v k 1 .
1
2 L2. 4 T
lY v k 1 .
X v 0 . l1. v k 1 .
2 L2. 4 T
q
l X v 0 . lY v k 1 .
2 l1. v 0 . l1. v k 1 .
1
ql X v 0 .
ql X v 0 .
2 L2. 4 T
l1. v 0 . Y v k 1 .
2 L2. 4 T
l1. v 0 . l1. v k 1 .
lY v k 1 .
1
L2. 4 T
q l X Y v 0 , v k 1 . 2.
2
l v 0 , v k 1 .
q
L2. 4 T
l X Y v 0 , v k1 . ,
2 l2. v 0 , v k 1 .
1
3.28.
rules as
X , Y ::v k s P X v 0 . , Y v k . .
1
1
P X v 0 . , Y v k1 . . f X Y v 0 , v k1 .
s f X Y v 0 , v k 1 . q f Y X v k 1 , v 0 . . 3.29.
LX Y v 0 , v k 1 .
l X Y v 0 , v k 1 .
L2. 4 T
l2. v 0 , v k 1 .
The variational condition for the frequency-dependent first-order multipliers gives an equation for
the first-order l-parameters:
0s
s
LX Y v 0 , v k 1 .
l X v 0 .
2 L2. 4 T
l1. v 0 . Y v k 1 .
q
2 L2. 4 T
l1. v 0 . l1. v k 1 .
lY v k 1 . . 3.32.
The variational criterion for the first-order parameters, in turn, determines the first-order multipliers:
0s
s
LX Y v 0 , v k 1 .
l X v 0 .
2 L2. 4 T
l1. v 0 . Y v k 1 .
q
2 L2. 4 T
lY v k 1 .
l1. v 0 . l1. v k 1 .
q lY v k 1 .
1.
2
2. 4
v k 1 . l
1.
v0 .
2 L2. 4 T
2 l1. v 0 . l1. v k 1 .
=l X v 0 . lY v k 1 . .
, 3.30.
LX Y v 0 , v k 1 .
L2. 4 T
0s
s
. 3.31.
l X Y v 0 , v k 1 .
l2. v 0 , v k 1 .
2 L2. 4 T
lY v k 1 .
X v 0 . l1. v k 1 .
3.34.
. 3.33.
3.35.
17
CHRISTIANSEN, JRGENSEN, AND HATTIG
TABLE I
Quadratic
X, Y ::v Y s
X , Y , Z ::v Y , v Z s
1
2
1
2
C " v P ( X ( v X ) , Y ( v Y )) h X q
C " v P ( X ( v X ) , Y ( v Y ) , Z ( v Z ))
ql X ( v X ) AY q
Cubic
X , Y , Z , U ::v Y , v Z , v U s
1
8
1
2
1
2
1
2
1
2
1
4
1
FX q
1
6
B ( v Y , v Z ) lY ( v Y ) l Z ( v Z )
G ( v Y , v Z ) l x ( v X ) lY ( v Y ) l Z ( v Z )
C " v P X v X . , Y v Y . , Z v Z . , U v U ..
F( v Z q vU ) l X Y ( v X , v Y ) l Z U ( v Z , vU ) q
q
F ( v Y ) l X ( v X ) lY ( v Y )
1
2
F XlY ( v Y ) l Z U ( v Z , v U )
G ( v Y , v Z q v U ) l X ( v X ) lY ( v Y ) l Z U ( v Z , v U )
l X ( v X )[ AY q B ( v Y , v Z q v U ) lY ( v Y )] l Z U ( v Z , v U )
2
1 x
1
q
G +
H ( v Y , v Z , v U ) l X ( v X ) lY ( v Y ) l Z ( v Z ) lU ( v U )
6
24
q
ql X ( v X )
1
2
BY q
1
6
C ( v Y , v Z , v U ) lY ( v Y ) l Z ( v Z ) lU ( v U )
a
The appropriate matrices are defined in Table IV, and the response equations are given in Table III. The permutation operator P is
defined in Eq. (3.29) and complex conjugation and the frequency sign inversion operator is defined in Eq. (3.35).
TABLE II
Linear
X, Y ::v Y = P X v X . , Y v Y .. h X q
Quadratic
X, Y, Z ::v Y , v Z s P X v X . , Y v Y . , Z v Z ..
Cubic
X, Y, Z, U ::v Y , v Z , v U s P X v X . , Y v Y . , Z v Z . , U v U ..
1
1
F v Z q v U . l X Y v X , v Y . l Z U v Z , v U . q F XlY v Y . l Z U v Z , v U .
8
2
1
X
Y
Z
U
q G v Y , v Z q v U . l v X . l v Y . l v Z , v U .
4
1 X
1
q
G q
H v Y , v Z , v U . l X v X . lY v Y . l Z v Z . lU v U .
6
24
F v Y . l X v X . lY v Y . s h XlY v Y .
1
2
FX q
1
6
G v Y , v Z . l X v X . lY v Y . l Z v Z .
The appropriate matrices are defined in Table IV, and the response equations are given in Table III. The permutation operator P is
defined in Eq. (3.29).
18
e 0. s 0
l(0)A(0) y h = 0
A v Y . lY v Y . q j Y = 0
lY v Y .Ayv Y . q hY q F v Y . lY v Y . = 0
A v Y q v Z . lY Z v Y , v Z .
qP Y v Y ., Z v Z .. AYl Z v Z . q
YZ
1
2
B v Y , v Z . lY v Y . l Z v Z . s 0
v Y , v Z .Ayv Y y v Z .
qP Y v Y ., Z v Z .. F Yl Z v Z . q
q
1
2
G v Y , v Z . lY v Y . l Z v Z .
F v Y q v Z . lY Z v Y , v Z . q lY v Y .w A Z q B v Z , v X . l Z v Z .x = 0
Variational theory
Zeroth-order equations
h=0
hY + F( v Y ) lY ( v Y ) = 0
F v Y q v Z . lY Z v Y , v Z .
qP Y v Y ., Z v Z .. F Yl Z v Z . q
1
2
G v Y , v Z . lY v Y . l Z v Z . = 0
The appropriate matrices are defined in Table IV, and the permutation operator P is defined in Eq. (3.29).
and references therein.. A 2 n q 1 rule was previously derived for monochromatic perturbations
see footnote 87 of w 21x. . We derive here the 2 n q 1
and 2 n q 2 rules for general frequency-dependent
response functions.
To derive the 2 n q 1 and 2 n q 2 rules, it is
convenient to introduce the not too short notations
LN s LV 0 , V1 ,? ? ?V ny 1 v 0 , v 1 , . . . , v ny1 . for the Fourier
components of the quasienergy Lagrangian
and l P s l V 1 ,? ? ?V p v 1 , . . . , v p . and l Q s
lV 1 ,? ? ?V q v
1 , . . . , v q . for the response amplitudes.
Bars and tildes are used to distinguish the operators and frequencies in the response vectors from
those of the Nth-order quasienergy derivative. The
multipliers can be treated in an analogous way.
The first derivative becomes
p
Introducing the frequency v s is1
v i and the
l v . notation of Eqs. 3.8. and 3.9., we obtain
using the chain rule:
LN
l
V 0 v 0 . V1 v . ??? V ny 1 v ny1 .
l v .
lV1 ,? ? ?V p v 1 , . . . , v p .
V 0 v 0 . V1 v 1 . ??? V ny 1 v ny1 .
p
= Vi vi .
is1
LN
l
L4 T
l v .
L4 T
.
l v .
3.37.
V 1 ,? ? ?V p
v1 , . . . , vp .
n L4 T
.
V 0 v 0 . V1 v 1 . ??? V ny 1 v ny1 .
3.36.
19
CHRISTIANSEN, JRGENSEN, AND HATTIG
TABLE IV
L4 T
u n y p.
l v .
p
= d V i V ny py 1q i d v i y v nypy1qi . . 3.38.
Derivative expression
is1
hY
1.
jY
2 (2) 4
v X . Y v Y .
2 L 2. 4 T
LN
l1. v X . Y v Y .
l P lQ
2 L 2. 4 T
A v Y .
l1. v X . l1. v Y .
3 L3 . 4 T
B v Y , v Z .
1.
C v Y , v Z , v U .
v X . l1. v Y . l1. v Z .
4 L4 . 4 T
F v Y .
l1. v X . l1. v Y .
3 L3 . 4 T
G v Y , v Z .
H v Y , v Z , v U .
4 L4 . 4 T
l1. v X . l1. v Y . l1. v Z . l1. v U .
3 L3 . 4 T
AZ
l1. v X . l1. v Y . Z v Z .
4 L4 . 4 T
BU
FZ
l1. v X . l1. v Y . Z v Z .
4 L4 . 4 T
GU
l0 .
a
Expressions for the matrices for a variational theory are
obtained simply by replacing L with Q. Matrices referring to
derivatives with respect to multipliers (e.g., A, B ??? ) are
identical zero for variational methods. The sum of the frequencies occurring in the derivative expressions is zero;
v X q v Y s 0, v X q v Y q v Z s 0 or v X q v Y q v Z q v U s 0.
otherwise 1, we obtain
LN
l P
s G0, 1, . . . , ny1.
=
20
ny p
V 0 v 0 . V1 v 1 . ??? V ny py 1 v nypy1 .
s G0, . . . , ny1.
ny pyq
V 0 v 0 . V1 v 1 . ??? V ny py qy 1 v nypyqy1 .
2 L4 T
=
u n y p y q.
l v . l v
.
p
= d V i V ny py 1q i d v i y v nypy1qi .
is1
q
= d Vj V ny py qy 1q j d v
j y v nypyqy1qj . ,
3.39.
js1
where v
s qis1 v i .
From Eq. 3.39., it is apparent that there exist
relations between the derivatives of LN with respect to l P and lQ for different n, p, and q and a
different set of operators and frequencies. It is
instructive here to compare them with the time-independent limit of Eq. 3.38. in the case where
there is only one external perturbations X:
LN
l
s G0 , 1, . . . , ny1.
ny p
X 0 ..
ny p
l0
. 3.40.
L0.
l0.
LX 0.
l X 0 .
L X Y yv Y , v Y .
l X Y yv Y , v Y .
s e 0. l0. . .
3.41.
The same comment also applies for the zerothorder multiplier equations. The same form of
equations for the first-order response equations are
obtained to each order, for example, the equation
for lY v Y . for a nonvariational method is determined from
0s
s
L X Y yv Y , v Y .
l X yv Y .
L X Y Z yv Y y v Z , v Y , v Z .
l X Z yv Y y v Z , v Z .
3.42.
L X Y yv Y , v Y .
L4 T
s
, 3.43.
Y
X yv Y . lv Y
l v Y .
L X Y Z yv Y y v Z , v Y , v Z .
lY Z v Y , v Z .
s
L4 T
X yv Y y v Z . lv Y q v Z
. 3.44.
21
CHRISTIANSEN, JRGENSEN, AND HATTIG
the variational criteria, we used the resulting equations to eliminate the terms that were not in accord
with the 2 n q 1 and 2 n q 2 rules. Having realized
this, in general, we know a priori that these terms
do not contribute. They can, thus, be safely ignored from the beginning of the derivation of the
response functions to any order. The lower-order
response equations can still be obtained according
to the variational criteria for the required responses. The use of a variational Lagrangian and
the 2 n q 1 and 2 n q 2 rules thus greatly simplify
the derivation, as can be seen by reexamining the
derivations in the previous subsections. We know,
for example, a priori, that the average value for a
molecular property in a nonvariational theory can
be evaluated from zeroth-order parameters and
multipliers, and we obtain straightforwardly Eq.
3.25. by simply ignoring all terms depending on
first-order responses. Similarly, for the determination of frequency-dependent second-order properties, we can from the outset discard the response
terms in Eq. 3.28. depending on second-order
parameters and multipliers and obtain the linear
response function directly in the form in Eq. 3.34..
3.F. SYMMETRY RELATIONS FOR THE
RESPONSE FUNCTIONS
The reduction from the nonvariational method
as given by Eqs. 3.30. ] 3.34. to a variational
method is obtained neglecting all terms containing
l and replacing L with Q. Equation 3.34. then
becomes
X , Y ::v Y
s P X v X . , Y v Y ..
2 Q 2. 4 T
=
lY v Y .
X v X . l1. v Y .
2 Q 2. 4 T
q
l X v X . lY v Y . .
2 l1. v X . l1. v Y .
3.45.
1
2 Q 2. 4 T
l1. v X . Y v Y .
2 Q 2. 4 T
q 1.
lY v Y . .
l v X . l1. v Y .
22
3.46.
2 Q 2. 4 T
lY v Y . .
X v X . l1. v Y .
3.47.
1
2
C"v
ql
where L t . is an anti-Hermitian operator. A selfconsistent field SCF. wave function can be described by the parametrization in Eq. 4.1. with the
operator L as w 3x
2 L2. 4 T
lY v Y .
X v X . l1. v Y .
vY .
2 L2. 4 T
X v X . l1. v Y .
4.1.
L t . s
l m t . qm y lUm t . qm . ,
4.2.
where qm
, qm . are orbital rotation generators
. 3.48.
qm
s Ep q s ap a a q a q ap b a q b ,
4.3.
L t . s
l m t . R m y lUm t . R m . ,
4.4.
m)0
4.5.
23
CHRISTIANSEN, JRGENSEN, AND HATTIG
CI approach can be described in terms of a
double-exponential parametrization and an appropriate set of orbital constraints: for example, the
SCF or multiconfigurational self-consistent field
MCSCF. equations. In this case, the wave function
is nonvariational in the orbital rotation parameters.. SCF response functions have been derived in
other contexts and implemented to high order w 27,
28, 42, 46]53x . Response functions for MCSCF wave
functions can be derived in an equivalent fashion
using a double-exponential unitary transformation
describing rotations in both the orbital and configuration spaces. Theory and implementation of
MCSCF response functions have been described in
detail in the literature in other contexts w 43, 54]57x .
Using a unified notation, Eqs. 4.2. and 4.4.
may be expressed as
L t . s
l m t . Q m y lUm t . Q m . s
lm t . Om ,
m
m)0
4.6.
where we have absorbed the summations over
excitation and deexcitation parts in one summation over both positive and negative m, such that
the definition of l m is extended to
lm s
lm
ylUm
m)0
m-0
4.7.
m)0
m - 0.
Q m
Qm
4.8.
s Hyi
Q t . s 0 exp yL t .. H y i
exp L t .. 0 .
4.9.
The determination of response functions and response equations follows now straightforwardly
from the quasienergy Q t .4T in agreement with
the expressions for the response functions, response equations, and matrices in Tables II]IV.
We shall here exemplify the derivation and subsequent analysis through second order.
24
exp L t ..
Hyi
Hyi
, L t .
, L t . , L t . q ???
4.10.
Hyi
t . . 4.11.
, L t . s w H , L t .x y iL
4.12.
Q 0. 4 T
l0.
i
s 0 w H0 , Oi x 0: . 4.13.
Q 1. t . s 0 < V t <0: .
4.14.
4.15.
where V 0 is the zero-frequency part of the perturbation in Eq. 2.3.. We obtain from Eq. 2.58. the
expectation value
X: s
Q 1. t .4 T
X 0 .
s 0 < X <0: .
4.16.
Q 2. t . s 0 w V t , L1. t .x q
1
2
H0 , L1. t .
1. t . , L1. t . 0 .
yiL
4.17.
2.
t. s
k1 , k 2
0 V v k 1 , L1. v k 2 .
H0 , L
1.
= 0 w H 0 , Oi x , Oj 0
yv k 1 L
k1
Fi j v Y . s yEiw2j x q v Y Siw2xj ,
v k 1 . , L1. v k 2 . 0 . 4.18.
1
Eiw2j x s y P Oi , Oj . 0 w H0 , Oi x , Oj 0 , 4.23.
2
Siw2j x s 0 w Oi , Oj x 0: .
4.24.
A
B*
B
,
A*
S
yD*
4.25.
D
.
yS*
4.26.
4.22.
v k1 .
0 Vy v k 1 , L1. v k i .
4.21.
E w2 x s
2 nq1 Q 2. t . 4 T s
qv Y 0 w Oi , Oj x 0: ,
S w2 x s
1.
P Oi v X . , Oj v Y . .
Introducing the ordering where index j is ordered with excitation before deexcitation j ) 0
before j - 0. and i is ordered deexcitation before
excitation i - 0 before i ) 0., we can write E w2 x
and S w2 x in the following form:
exp yi v k 1 q v k 2 . t .
H0 , L1. yv k 1 .
w H 0 , Oi x , Oj 0 s y 0 w Oi , Oj x , H 0 0
y0
s y0
w Oj , H 0 x , Oi
Oi , w H 0 , Oj x
;
0;
0;.
4.27.
qv k 1 L1. yv k 1 . , L1. v k 1 . 0 .
4.19.
c km n 0 w Ok , H0 x
0:
hiY
2 Q 2. 4 T
s 1.
s 0 w Y , Oi x 0: , 4.20.
l i v X . Y v Y .
Fi j v Y . s
2 Q 2. 4 T
v X . l1.
vY .
l1.
i
j
s 0.
4.28.
25
CHRISTIANSEN, JRGENSEN, AND HATTIG
variational criteria. The matrices A, B, S, and D
can now be written in the form
A i j s 0 Q i , H0 , Q j
0 ,
4.29.
Bi j s 0 Q i , w H 0 , Q j x 0 ,
4.30.
S i j s 0 Q i , Q j 0 ,
4.31.
D i j s 0 w Q i , Q j x 0: .
4.32.
Y
hyi
0 w Y , Q i x 0:
/
hiY
0 Y,
Q i
0:
4.33.
lY v Y . s y F v Y ..
y1
hY,
4.34.
H 0 < i : s Ei < i : .
lY v Y . s E w2x y v Y S w2x .
y1
gY.
hiXlYi v Y . .
"i
4.37.
4.35.
4.36.
4.38.
TABLE V
Vectors and matrices for a single exponential parametrized variational wave function.a
Quantity
hmY
Fi j v Y .
Gi jk v Y , v Z .
Hi jkl v Y , v Z , v U .
Fi Zj
GiUjk
hi
0 <w Y, Oi x<0:
1
P(O i v X ., Oj v Y ..w 0 w w H0 , Oi x , Oj x 0: q v Y 0 <w Oi , Oj x <0:x
2
1
P ( Oi ( v X ), Oj ( v Y ), Ok (u Z ))[ 0 [[[ H0 , Oi ] , Oj ] , Ok ] 0:
6
+( v Y + v Z ) 0 [[ Oi , Oj ] , Ok ] 0: ]
1
P ( Oi v X ., Oj v Y .,Ok v Z ., Ol v U .w 0 w w w w H0 , Oi x , Oj x , Ok x , Ol x 0:
24
q v Y q v Z q v U . 0 w w w Oi , Oj x , Ok x , Ol x 0: x
1
P ( Oi , Oj ) 0 [[ Z, Oi ] , Oj ] 0:
2
1
P ( Oi , Oj , Ok ) 0 [[[ U, Oi ] , Oj ] , Ok ] 0:
6
0 <w H0 , Oi x<0:
26
4.39.
the expression in Table V introducing the statetransfer operators. The quadratic response function
becomes
X ; Y , Z ::v Y , v Z syP X v X . , Y v Y . , Z v Z ..
4.40.
i , j)0
v X q v i . v Z y v j .
and
4.45.
Bi j s 0 w <0: i < , w H0 , <0: j <x x 0: s 0. 4.41.
where
Y s Y y 0 < Y <0: .
hiY
/
s
hiY
y i < Y <0:
.
0 < Y < i :
4.42.
Y
v i y v Y . lqi
vY .
y i < Y <0:
s
. 4.43.
Y
0 < Y < i :
v i q v Y . lyi v Y .
= y
i)0
i)0
v Y q vi
s P X v X . , Y v Y ..
=
i , j, k)0
v Y y vi
i)0
i)0
v Y y vi
. 4.44.
4.46.
j)0
vU y vj .
/5
4.47.
v Y v f
4.48.
where we have introduced the transition strength
matrix S Xo fY and the left and right first-order transition matrix elements
TfYo s f < Y <0: ,
4.49.
4.50.
The left and right transition moments for a Hermitian operator are related to each other by a com-
27
CHRISTIANSEN, JRGENSEN, AND HATTIG
plex conjugation: ToYf s TfYo .*. The residue for the
linear response function at v Y s yv f is easily
obtained by interchanging the X and Y operators
and related frequencies v Y and v X in Eq. 4.48.:
lim
v Yy v f
q
4.51.
1
2
v Z v f
s yToXf Y yv Y . TfZo ,
4.53.
j)0
vj y vX
4.55.
lim
v Zy v f
v Z q v f . X ; Y , Z ::v Y , v Z
s ToZf Tf Xo Y v Y . ,
4.56.
where
Tf Xo Y v Y . s ToXf Y yv Y . . *.
4.57.
1
2
Z XY
vY
o f Tf o
v Y v i
lim
v Zy v f
v Z q v f . X ; Y , Z ::v Y , v Z
s yToZf Tf Xi TfYo ,
4.59.
where
,
4.54.
28
vj y v Y
jG0
vj y vX
jG0
v Y q v f . X , Y ::v Y
s yToYf Tf Xo s y S Xo f, Y . *.
ToXf Y yv Y
4.60.
The residue for v X s v i is obtained by interchanging X and Y. The residue of Eq. 4.56. gives
second-order transitions:
lim
v Yy v i
lim
v Y q vi .
v Zq v U v f
lim v Z y v f . X ; Y , Z ::v Y , v Z
v Z v f
s yToYi Ti Xf TfZo .
S Xo fY s Ti Xf TfYi s
1
2
1
2
X :o q X :Uo .
1
2
Ti iX q Ti iX . * . .
4.63.
v Y v i
lim v Z y v f . X ; Y , Z ::v Y , v Z s 0
v Z v f
4.64.
gives zero for an exact state unless there exist a
state j such that the difference in energy between
states j and i is equal to the excitation energy for
state f : v f s v j y v i ..
The cubic response function has poles where the
absolute value of one of the three external frequencies is equal to an excitation energy, v Y s "v f ,
v Z s "v f , or v U s "v f , or when the sums of
two or three of these frequencies are equal to an
excitation energy. For later reference, we note that
the following residue search in the cubic response
function gives information on the cross section for
1
2
XY
yv Y
of
. TfZU
vU .
o
XY
q ToZU
v Y .*
f . Tf o
' S Xo fY , ZU v Y , v U . .
4.65.
4.61.
where the second equality is again somewhat redundant in exact theory but will be useful for the
discussion of approximate theories. For i s f, Eq.
4.60. contains information on the difference of
first-order properties in the excited state and in the
ground state:
X :i s X :o q Ti iX s
vU .
s ToXf Y yv Y . TfZU
o
v Z qv U yv f . X ; Y , Z, U ::yv Y , v Z , v U
4.66.
29
CHRISTIANSEN, JRGENSEN, AND HATTIG
the specific ordering of the excitation and deexcitation operators is used where the matrices E w2 x and
S w2 x have the structure in Eqs. 4.25., 4.26., and
4.29. ] 4.32.. The paired structure is thus obtained
for a single exponential variational ansatz for the
wave function for any kind of operator manifold.
The eigenvalue equation Eq. 4.66. only determines the eigenvector within a normalization. We
require that the eigenvectors in U satisfy the normalization condition,
v Y v f
lim
v Yy v f
TfYo s y UiyfhiY ,
v
w2x
U S U s s,
U E w2x U s v ,
s V s v.
4.69.
s U v y v Y s .
y1
U . 4.70.
30
hiY Ui f .
4.74.
"i
v Y v f
lim
v Yy v k
v Y q v k . X , Y ::v Y s yv ToYf v Tf Xo .
4.76.
4.68.
E w2x y v Y S w2x .
ToYf s
4.67.
4.73.
"i
sv ToXf v TfYo s
1
2
v Z v f
s yv ToXf Y yv Y . v TfZo ,
lim
v Zy v f
4.78.
v Z q v f . X ; Y , Z ::v Y , v Z
sv ToZf v Tf Xo Y v Y . ,
4.79.
ToXf Y yv Y .
s yP X v X . , Y v Y ..
= FX q
1
2
G yv Y , v f . l X yv X .
=lY yv Y . U f ,
v
4.80.
Tf Xo Y v X , v Y .
s P X v X . , Y v Y ..
= FX q
1
2
G v Y , yv f . l X v X .
=lY v Y . Uyf ,
4.81.
v Y v i
lim
v Zy v f
v Z q v f . X ; Y , Z ::v Y , v Z
s yv ToZf v Tf Xi v TioY ,
lim
v Yy v i
4.82.
v Y q vi .
lim v Z y v f . X ; Y , Z ::v Y , v Z
v Z v f
v
sy
ToYi v Ti Xf v TfZo ,
4.83.
where
v
Ti Xf s F X q G yv i , v f . l X v i y v f . . Uyi U f .
4.84.
31
CHRISTIANSEN, JRGENSEN, AND HATTIG
tion and the 2 n q 1 rules refer to the ground-state
properties. In response theory, the excited state is
obtained not from a variational calculation on the
excited state, but from a variational calculation on
the ground state followed by a solution for the
appropriate root in a generalized eigenvalue equation. The excited states as described by response
theory for a variational model for the ground state
are not variational. While the expressions for transition properties obtained directly from the
residues appears to be computationally efficient,
those for calculations of properties in the excited
state are not. We will here investigate this issue a
bit further. It seems natural to take the energy of
the excited state to be
E f s Eo q v f .
4.87.
L f s Eo q U f . E w2x U f
q a U f . S w2x U f y 1 . q l fh ,
32
0s
4.86.
v f s U f . E w2x U f ,
4.88.
dL f
0s
0s
0s
da
dL f
dU
dl f
s h,
4.90.
s E w2x U f q aS w2x U f ,
4.89.
s U f . S w2x U f y 1,
dL f
d U f .
dL f
4.91.
and
0s
dL f
dl
dE0
dl
q U f .
q a U f .
dE w2 x
dl
Uf
dS w2 x
dl
U f q lf
dh
dl
4.93.
w2 x
E0
h
E
q U f .
U fql f
,
.
X 0
X 0
X 0 .
4.94.
lE
w2x
s yU f .
dE w2 x
dl
U f,
4.95.
33
CHRISTIANSEN, JRGENSEN, AND HATTIG
functions or by differentiation of the total energy
of the excited state as described previously in this
subsection.
5.2.
34
T t. s
Ti t . s tm t . tm .
i
i , mi
is1
5.3.
5.4.
5.5.
s 0.
&
yF t . <CC t .:
5.7.
Q t . s F t . s R H y i
&
&
CC t .
s R < H <CC t .: .
5.8.
m i exp yT t .. H y i
&
From the considerations in Section 2 w in particular, the discussion following Eqs. 2.67. ] 2.69.x , it
is clear that the CC quasienergy is not necessarily
real. We should have this in mind and ensure that
the expressions for molecular properties satisfy the
symmetry relations in Eqs. 2.19. ] 2.22.. We thus
have to apply the symmetrization procedure in
Eqs. 2.70. ] 2.73. using the symmetrization operator C " v in Eq. 3.35..
5.B. CC RESPONSE FUNCTIONS
The zeroth-order Lagrangian becomes
CC t . s 0. 5.9.
The time-dependent cluster amplitudes are obtained without reference to Q t .. When the cluster
amplitudes have been found, Q t . can be obtained
from Eq. 5.8.. It is noted that in the time-independent limit Eq. 5.9. reduces to the usual cluster
amplitude equations
Vm i s m i <exp yT . H exp T . < R : s 0 5.10.
and Eq. 5.8. becomes the usual CC ground-state
energy
E0 s R < H exp T . < R : .
L < s R < q
tm t .
i, mi
0s
m i vexp yT t .. H y i
=exp T t .. R .
tm0. mi <expyT 0. .
i, mi
L0.
tm0.i
5.12.
From this point, the determination of the CC response functions and response equations is a simple application of the theory developed in the
preceding sections. For approximate CC models,
response functions are simply obtained by introducing the corresponding approximated CC equations as constraints in the Lagrangian. The above
procedure can be applied to any CC model with a
well-defined quasienergy and with well-defined
time-dependent amplitude equations. This is crucial for using the theory for, for example, the CC2
and CC3 models as discussed before w 67, 68x .
. 5.15.
The variational condition with respect to the zeroth-order Lagrangian multipliers gives the cluster
amplitude equations
5.14.
as well as the auxiliary combination of the projection onto the reference state and the transformed
excited configurations:
5.11.
5.13.
5.16.
and the variational condition for the amplitudes
determines the zeroth-order multipliers
0s
L0.
tn0.j
s L H0 , tn j CC
s R< q
tm0. mi <expyT 0. .
i, mi
= H0 , tn j < CC : .
/
5.17.
35
CHRISTIANSEN, JRGENSEN, AND HATTIG
Equation 5.17. ensures that the Lagrangian is variational with respect to the cluster amplitudes,
thereby giving an equation for the multipliers.
Following the outline in Section 3 for nonvariational methods, we obtain the standard expressions for an expectation value in CC theory:
pq
s
X: s
L
1.
t .4 T
X0.
1
2
1
2
s L < X < CC : .
Consider the case where the reference wave function is purely real. For a one-electron operator, the
expectation value in the form in Eq. 5.18. can
be written in terms of a real asymmetric density
matrix D:
Dp q s L < Ep q < CC : .
5.20.
Dp q X p q ,
pq
36
5.22.
5.18.
X: s
2 Dp q q Dq p . X p q .
pq
Dp q 2 X p q q X pUq .
5.21.
5.23.
0. .
H0 , tn j CC , 5.24.
1
2
H0 , T 1. yv k . , T 1. v k . CC
y tm1.i yv k . v k tm1.i v k .
mi
q tm1.i yv k . m i V v k
mi
hn j s R H0 , tn j CC .
5.25.
q H0 , T 1. v k . CC: .
5.28.
2 nq1 L2. t .4 T
s
L w V t , T 1. t .x
5.29.
tm1. t . tm1. t .
i
i, mi
tm1. t . mi V t q
i, mi
H0 , T 1. t . CC: .
A y v Y I . t Y v Y . q j Y s 0,
5.26.
m i < s m i <exp yT 0. . .
5.27.
ksyn
L Vyv k , T 1. v k .
5.30.
2 L2. 4 T
s Am in j y v Y dm in j ,
tm1.i v X . tn1.j v Y .
H0 , T 1. t . , T 1. t . CC
yi
Am in j v Y . s
t Y v Y . A q v Y I . q h Y q F t Y v Y . s 0. 5.31.
for the first-order multipliers. We have here introduced the CC vectors j Y and h Y and the matrix F.
They arise naturally from the derivative expressions in Table IV and specialized expressions for
CC theory are compiled in Table VI. We note that
the expressions in Table VI are valid for models
where the cluster expansion has been truncated,
but do not apply for models where, in addition,
approximations have been introduced in the
ground-state CC amplitude equations. Thus, they
are adequate for CCS, CCSD, and CCSDT, but, for
example, not strictly valid for CC2 and CC3 w 67,
68x . Note that this is not due to restrictions in the
theory, but a limitation of the notation introduced
for the sake of conciseness. For models like CC2
and CC3, the appropriate expressions are easily
obtained by returning to the derivative definitions
in Table IV and tracing the approximations introduced in the cluster equations to the relevant matrices. The present approach is thus well defined
for any iterative CC model.
The linear response functions for any iterative
CC model can be written in the common form
37
CHRISTIANSEN, JRGENSEN, AND HATTIG
TABLE VI
hmY
jmY
Amn
Bmns
Cmnsd
Fmn
Gmns
Hmnsd
Z
Amn
U
Bmns
Z
Fmn
U
Gmns
hn
note that in CC theory the F-matrix becomes independent of the frequencies. This follows from the
fact that the excitation operators commute and,
therefore, terms like w T 1. t ., T1. t .x vanish identically. All matrices defined using two or more
differentiations with respect to the cluster amplitudes on the CC quasienergy do not contain any
frequency dependence. This is the case for the
F, G, H and B, C, D matrices. Therefore, the
quadratic CC response function can be written in
the following rather compact form using the expressions in Table I:
X , Y , Z ::v Y , v Z
s
1
2
C " v P X v X . , Y v Y . , Z v Z ..
1
2
C " v P X v X . , Y v Y ..
= hX q
1
2
Ft X vX . tY v Y . .
5.32.
38
1
2
FX q
1
6
G t X vX . tY v Y .
qt X v X . AY q
1
2
Bt Y v Y .
t Z vZ . .
5.33.
V i j s v i di j .
5.34.
The columns of R thus contain the right eigenvectors of A, and the rows of L contain the left
eigenvectors. When the eigenvectors span the complete space L s Ry1 , we will denote single eigenvectors with eigenvalue v f as R f and L f : Rmf i s
Rm i f , Lmf i s L f m i . Transformation to the representation where the Jacobian is diagonal w Eq. 5.34.x
implies a transformation of the right operator manifoldthe excitation operatorsto the diagonal
tk s
tm Rmk
i, mi
5.35.
Lmk tm .
i, mi
5.36.
d Y
tk v Y
sdj kY .
1
2
hkX dj kY
v
k
y vk
2
kn
5.39.
L fA s v f L f ,
5.40.
C " v P X yv Y . , Y v Y ..
A R f s vf R f
or the left
5.37.
d Xd
j k Fk n dj nY
v Y q v k . v Y y v n .
5.38.
It is evident from Eq. 5.38. that the CC linear
response function has poles when v Y s "v k ,
where v k is one of the eigenvalues of the CC
Jacobian. We note that relative to the exact linear
response function in the diagonal representation in
Eq. 4.44. the CC linear response function has an
additional termthe F matrix term. As discussed
in Section 3, this term can be eliminated for variational theories and thus also exact theory. while
this is only possible in nonvariational theory at the
expense of introducing the first-order response of
the Lagrangian multipliers. However, we observe
that in the case of the CC linear response function
as derived from the Lagrangian in Eq. 5.12. the
extra F term does not give additional poles and
that the poles are only first order. As we will
discuss later in this section, this is not so for many
other nonvariational approaches, and these response functions thus do not have a correct pole
structure that can be used for an unambiguous
identification of excitation energies and transition
properties. The pole structure of the CC linear
5.41.
39
CHRISTIANSEN, JRGENSEN, AND HATTIG
course, is trivial to back transform the residues to
the original basis of excitation and deexcitation
operators. We will instead take a route where we
first determine the residues of the response vectors, and subsequently use those to determine the
residues of the response functions. This gives a
more transparent structure of the equations and
expresses the equations in the original basis of
excitation and deexcitation operators where the
calculations are carried out. Let us initially introduce the scalar quantities
cc
cc
ToYf
TfYo
d
sdj fY
h q Ft
h q Ft
yv f .
5.42.
f
yv f . R .
f
5.43.
The reason for the notation will soon become apparent. Furthermore, we introduce the auxiliary
vector
M f v f . s y FR f . v f 1 q A.
y1
5.44.
v Y v f
lim
v Yy v f
v Y q v f . t Y v Y . s 0,
5.46.
v Y v f
lim
v Yy v f
v Y q v f . t Y v Y . s ycc TofY v f . L f .
5.48.
40
lim v Y y v f . X , Y :: v Y
v Y v f
1
2
cc
5.49.
lim v Y q v f . X , Y :: v Y
v Y v f
sy
s L j .,
f
1
2
cc
s y cc S Xo fY . *,
/
5.50.
lim
lim v Z y v f . X ; Y , Z ::yv Y , v Z
v Yy v i
v Z v f
sy
cc
cc
XY
ToXf Y yv Y . TfZo q cc ToZcc
v Y . .* ,
f Tf o
v Y q vi .
lim v Z y v f . X ; Y , Z ::v Y , v Z
v Z v f
sy
5.51.
1
2
cc
5.55.
v Zy v f
v Z q v f . X ; Y , Z ::v Y , v Z
cc
XY
ToZcc
vY . q
f Tf o
cc
where
cc
//
AX q
1
2
cc
ToXf Y yv Y . TfZo * .
5.52.
cc
Bt X v X . t Y v Y . ,
Ti Xf s Li AX q Bt X v i y v f . . R f . 5.56.
5.53.
cc
S Xi f Y s
ToXf Y yv Y .
FX q
1
2
G t X yv X . t Y yv Y .
qt X yv X . AY q Bt Y yv Y .
qM f v f . AX q
1
2
cc
in analogy with the explicitly symmetrized expressions of exact theory w Eq. 4.62.x . Note that
this expression has the Hermitian property
cc S Xi f Y .* scc SYi fX , while this is not true for the
primitive produce cc Ti Xf cc TfYi .* /cc TiYf cc Tf Xi .
Finally, we note the residue search of the
quadratic response function
s yP X v X . , Y v Y ..
=
Rf
Bt X yv X . t Y yv Y . ,
lim v Y y v i .
v Y v i
5.54.
where v X s v f y v Y . As for the linear response
functions, the residues do, in principle, not allow
for a determination of transition matrix elements;
however, the structure is suggestivewe have
different left and right transition matrix elements
and expect again that the correct expression for the
molecular property is obtained by an appropriate
symmetrization. We will see this confirmed when
lim v Z y v f . X ; Y , Z ::v Y , v Z
v Z v f
/ 0.
5.58.
Thus, there exists a residue search that gives identically zero for the exact quadratic response function but a nonvanishing result for the CC quadratic
response function. This is similar to SCF see
Section 4..
41
CHRISTIANSEN, JRGENSEN, AND HATTIG
5.D. ALTERNATIVE EXPRESSIONS FOR
RESPONSE FUNCTIONS AND RESIDUES IN
CC THEORY
In this subsection, we discuss alternative forms
of the response functions and residues with emphasis on the differences in structure and computational requirements. The CC linear response in
Eq. 5.32. can be rewritten in an asymmetric form
requiring only response equations with respect to
the perturbation Y to be solved:
X , Y :: v Y s
1
2
C " v h X tY v Y . q tY v Y . j X .
5.59.
ToYf s h Y R f q M f v f . j Y .
5.60.
Using the interchange technique, the two different forms of cc ToYf in Eqs. 5.43. and 5.61. are seen
to be equivalent w M f v f . j Y syFR f v f 1qA.y1 =
j Y s FR f t Y yv f . s F t Y yv f . R f x . Consider now
the calculation of the transition strength using Eq.
5.49. together with either Eqs. 5.42. and 5.43. or
Eq. 5.42. in combination with Eq. 5.60.. Using the
first set of equations, we need to solve for
f
R f , L f , t Y yv f ., and t X yv f ..* to calculate cc S Xo Y ;
f
while using the latter, we need to solve for R , L f ,
and M f. The latter form thus requires only the
solution of one set of equations for M f to deterf
mine cc S Xo Y for all operator sets, while the first
requires the solution of first-order response equations for each different operator X or Y. Thus, M f
has the role of a Lagrangian multiplier. For X s Y
s a real operator, the same number of equations
must be solved using either of the two approaches;
in all other cases, the approach utilizing the M f
vector is the most efficient. The apparent paradox
is therefore that the 2 n q 1 and 2 n q 2 rule expressions for the linear response function give
first-order transition matrix elements that are not
in accord with the 2 n q 1 rule, while the expression that does not fulfill the 2 n q 2 rule for the
42
v Zq v U v f
v Z q v U y v f . X ; Y , Z, U ::yv Y , v Z , v U
cc
cc
vU .
TofX Y yv Y . TfZU
o
cc
yv U . Tf Xo Y v Y . * .
ToZU
f
cc
5.61.
//
cc X Y
Tf o v Y . is found in the same form as in Eq.
5.53., while cc ToXf Y yv Y . becomes
cc
ToXf Y yv Y .
s y P X v X . , Y v Y ..
=
FX q
1
2
G t X yv X . t Y yv Y .
qt X yv X . AY q Bt Y yv Y .
qFt X Y yv X , yv Y . R f .
Rf
5.62.
nique:
cc
Ti Xf s Li AX q Bt X v i y v f . . R f
i X f
s LA
R y Li B R f . A q v f y v i . 1 . j X
i X f
s LA
R q N i f O vi , v f . j X ,
F t X Y yv X , yv Y . R f
s FR f t X Y yv X , yv Y .
where
s y FR . A q v X q v Y . 1 .
f
= AX q
1
2
y1
N i f v i , v f . A q v f y v i . 1 . q Li B R f s 0.
5.65.
Bt X yv X . t Y yv Y .
s M f v X q v Y . AX q
=t Y yv Y . .
5.64.
1
2
Bt X yv X .
5.63.
43
CHRISTIANSEN, JRGENSEN, AND HATTIG
state is determined. Usually, the Hartree]Fock
HF. state is chosen as the reference state. Thus,
we require that
0 s e m n k . s HF <w Em n , H0 x <HF:
v f s L fA t , k . R f .
5.67.
tmf Vm t , k .
i, mi
q a L f R f y 1. q
k mf n e m n k . .
5.68.
mn
44
dL f
dL f
dL f
s L f R f y 1,
5.69.
s A t , k . R f q a R f ,
5.70.
da
dR f
0s
dL f
dtn j
s L fA t , k . q a L f ,
dL f
0s
5.66.
dL f
0s
s Vm i t , k . ,
dtmf i
dEo t , k .
dtn j
q Lf
dA t , k .
tmf
0s
dL f
dkm n
dL f
d k mf n
dVm i t , k .
dtn j
5.73.
s em n k . ,
dEo t , k .
dkm n
q
5.72.
Rf
dtn j
i, mi
0s
5.71.
tmf
i, mi
q Lf
5.74.
dA t , k .
dkm n
Rf
dVm i t , k .
dkm n
de p q k .
q k pf q
dkm n
pq
5.75.
1
2
C"v
tmf
i, mi
Eo t , k .
A t , k .
X
Rf
Vm i t , k .
i
q k mf n
mn
q Lf
X
em n k .
X
/
VOL. 68, NO. 1
1
2
C"v
Eo t , k .
X
q k mf n
mn
em n k .
X
tmf jmX
q L fAX R f q
i, mi
5.76.
1
2
C"v
Eo t , k .
X
q L fAX R f q
tmf jmX
mi
5.77.
The expression Eq. 5.77. is equivalent to the expression obtained by adding the ground-state
first-order property w Eq. 5.19.x to the expression
found w Eq. 5.56. with i s f x from the residue of
the quadratic response function if we apply the
C " v symmetrizations in Eq. 4.63.:
X :f s X : 0 q X y X :f
s
1
2
C"v
Eo t , k .
X
q t 0.j X
qL fAX R f q L f Bt X R f
s
1
2
C"v
Eo t , k .
X
q L fAX R f
q t 0. y L f B R fAy1 . j X ,
5.78.
where t 0. are the ground-state zeroth-order multipliers. Since Eq. 5.73. can be expressed as
t f s t 0. y L f B R fAy1 s y h q L f B R f . Ay1 ,
5.79.
it is seen that Eq. 5.78. is equivalent to Eq. 5.77..
In the case where we do not include orbital relaxation in the Lagrangian in Eq. 5.68., the two
derivsations thus agree as they should in a consistent theory. We note that the structure of Eq. 5.77.
is similar to the one obtained in variational theory,
Eq. 4.94..
We may summarize the above discussion as
follows: For calculation of excited-state first-order
45
CHRISTIANSEN, JRGENSEN, AND HATTIG
Higher-order derivatives can be found easily by
taking the second derivative of the excited-state
Lagrangian in Eq. 5.68. and allows for an analytical calculation of second-order static. properties
in the excited statemost notable, the molecular
Hessian.
The procedure that we have used in this section
exemplifies the generality of the Lagrangian technique. If we know how to calculate some property
including the equations that must be solved, we
can construct a property-oriented Lagrangian, allowing all derivatives of this property to be obtained easily and in a form that satisfies the 2 n q 1
and 2 n q 2 rules. In this case, the property is the
excited-state energy obtained from the linear response eigenvalue equation in combination with
the ground-state energy. The excited-state Lagrangian w Eq. 5.69.x is the carrier functional for the
determination of static excited-state properties.
5.F. ORBITAL RELAXED CC RESPONSE
THEORY AND SECOND-ORDER
MLLER]PLESSET PERTURBATION THEORY
We may include orbital relaxation explicitly in
the time-dependent CC quasienergy Lagrangian,
modifying the Lagrangian in Eq. 5.12. to
L cc s HF exp yk t .. H y i
exp k t ..
=exp T t .. HF
= Hyi
exp k t .. exp T t .. HF
q k m n t . HF Em n , exp yk t ..
mn
= Hyi
exp k t .. HF .
5.80.
46
X ; Y :: v Y
s
s
2 L4 T
X v X . Y v Y .
1
2
s0
C " v P X v X . , Y v Y ..
= L I X Y vX , v Y .
q I X v X . , T Y v Y . CC:
q
1
2
H0 , T X v X . , T Y v Y . CC:
q k m0.n HF Em n , I X Y v X , v Y . HF: ,
mn
5.81.
where we have introduced
I Y v Y . s Y q H0 , k Y v Y . y v Y k Y v Y . ,
5.82.
I X Y vX , v Y .
s
1
2
P X v X . , Y v Y ..
q
q
q tm i t . m i exp yT t .. exp yk t ..
mi
1
2
vY
2
X, kY vY .
H0 , k X v X . , k Y v Y .
k X vX . , k Y v Y .
5.83.
The equation determining the first-order clusters parameters is equivalent to Eq. 5.30. with the
only modification that the right-hand side of the
cluster amplitude response equation is modified to
5.85.
We can now discuss some structural differences
between the orbital relaxed form in Eq. 5.81. and
1
2
C " v P X v X . , Y v Y ..
= L X , T Y v Y . CC:
q
1
2
H0 , T X v X . , T Y v Y . CC: ,
5.86.
47
CHRISTIANSEN, JRGENSEN, AND HATTIG
nowned CCSDT. method will be even more dubious. In CCSDT., a perturbational correction for
the effect of triples excitations is added to the
CCSD energy. The perturbational correction is defined assuming HF orbitals and thus requires orbital relaxation to be included. A CCSDT. linear
response property will thus have both SCF and
CCSD poles where the SCF poles are of secondorder nature. as well as poles corresponding to the
triples excitations. Even if the orbital constraint
could be relaxed, the poles would still be of CCSD
quality: Only iterative models can give response
functions with a pole structure that is consistent
with exact theory. It is, of course, possible to define perturbational corrections to, for example, CCS
or CCSD excitation energies w 80x ; however, it
should be emphasized that the excitation energies
obtained in such an approach are not the poles of
any response function. Thus, there will always
formally be a lack of consistency between the
ground-state energy and the excitation energy in
such an approach. Each is defined using a procedure that is independent of the other.
As another example, we discuss briefly the
Brueckner coupled cluster BCC. theory. In the CC
theory, the cluster parameters and the orbital rotation parameters are treated at equal footing in a
one-step approach:
48
L MP 2 s HF exp yk t .. H y i
exp k t ..
= 1 q T2 t .. HF
q tm 2 t . m 2 exp yk t .. H y i
m2
=exp k t .. HF
q tm 2 t . m 2 exp yk t .. F y i
m2
=exp k t .. , T2 t . HF
q k m n t . HF Em n , exp yk t ..
mn
= Hyi
exp k t .. HF .
5.88.
Q t . s
0 Hyi
/ ;
0 .
6.1.
In time-dependent theory, the generalized variational principle and the generalized Hellmann]
Feynman theorem can be written in terms of the
time-dependent quasienergy:
d Q t . q i
6. Summary
For exact theory, many different routes may be
taken to derive abstract expressions for the determination of molecular properties. However, for
approximate theories, considerably more care is
needed since many relations that are trivially fulfilled in exact theory are no longer satisfied. Furthermore, with actual calculations in mind, it also
becomes crucial to minimize the number of equa-
0<d
0: s 0
6.2.
and
0 < X <
0:exp yi v t . s
Q t .
0
0
qi
.
x v .
t
x v .
6.3.
49
CHRISTIANSEN, JRGENSEN, AND HATTIG
is equivalent to the time-dependent Schrodinger
d Q t .4 T s 0
6.4.
Q t .4 T
s
0 < X <
0:exp yi v t . 4 T ,
x v .
6.5.
50
ACKNOWLEDGMENTS
This work was supported by the Danish Natural Science Research Council Grant No. 11-0924..
We acknowledge discussions with Henrik Koch
and Jurgen
Gauss. C. H. is indebted to the Deutsche
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32. S. I. Chu, Adv. At. Mol. Phys. 21, 197 1985..
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