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An alternative approach for the calculation of the electron-positron 共e-p兲 contribution to magnetic
properties based on two-component Breit–Pauli spinors is presented. In it, the elimination of the
small component scheme is applied to the inverse propagator matrix of e-p pairs. The effect of the
positronic manifold is expressed as an operator acting on Breit–Pauli spinors. The operator form
thus obtained sums up the relativistic correction as a geometric series and as a result a totally
different behavior in the vicinity of a nucleus is obtained as compared to the one of the linear
response approximation. This feature has deep influence in numerical values of the e-p contribution
to the nuclear magnetic shielding of heavy atoms. Numerical calculations carried out for Kr, Xe, and
I show that with this approach, the e-p contributions to this property are in good agreement with
those of four-component methods. © 2009 American Institute of Physics.
关DOI: 10.1063/1.3063639兴
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084102-2 Zaccari et al. J. Chem. Phys. 130, 084102 共2009兲
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084102-3 Geometric ESC approach of magnetic properties J. Chem. Phys. 130, 084102 共2009兲
Taking into account that the Hamiltonian under consideration present work we intend to develop an approximation of order
is a one-body Hamiltonian, the propagator has a straightfor- 1 / c2 to the inverse polarization propagator 共PP兲 matrix,
ward expression in terms of the corresponding eigenstates keeping it in the denominator of Eq. 共15兲. This procedure
and eigenvalues: sums the relativistic effects as a geometric series of the first
order correction, in close resemblance to the RPA approxi-
Pep,e⬘p⬘ = ␦e,e⬘␦ p,p⬘共Ee + E p兲.
−1
共7兲
mation. Therefore, it is expected to bring calculated results
In this case, Eb can be re-expressed as closer to four-component RPA ones.
In what follows a fixed electronic state is assumed and
Eb = 兺 兺 具e兩␣ · A兩p典Pep,ep具p兩␣ · A兩e典. 共8兲 the whole positronic contribution is added up. To this end we
eocc p consider matrix 共1 + M共e兲兲, Eq. 共17兲. Consistently to order
This is our starting point to obtain the nonrelativistic c−2 the eigenvalue E⬘p can be replaced by the nonrelativistic
limit and the leading order relativistic correction coming limit of the Dirac equation for positrons. We start from
from these terms. The Dirac 共or Dirac–Fock兲 Hamiltonian
− 共HD + mc21兲 p = E⬘p p . 共18兲
for electrons and positrons can be expressed as
共HD − mc2兲e = Ee⬘e , 共9兲 Separating into upper 共U兲 and lower 共L兲 components, the
following is obtained:
− 共HD + mc2兲 p = E⬘p p . 共10兲
− 共共2mc2 + V兲Up + c共 · p兲Lp 兲 = E⬘pUp , 共19兲
The leading order in the energy E is given by the rest mass of
the electron and positron, and the difference, represented by − 共c共 · p兲Up + VLp 兲 = E⬘pLp . 共20兲
E⬘, which depends strictly on the states involved, will be
considered as a perturbation. As a consequence the propaga- As it is seen, in this case Up plays the role of the small
tor can be separated accordingly: component and Lp is the large one. Following the standard
−1 共0兲−1 共1兲−1
ESC scheme the following is obtained at the lowest order:
Pep,e⬘p⬘ = Pep,e⬘p⬘ + Pep,e⬘p⬘ , 共11兲
·p L
共0兲−1 Up = − , 共21兲
Pep,e⬘p⬘ = 2mc ␦e,e⬘␦ p,p⬘ ,
2
共12兲 2mc p
E⬘ + E⬘
M ep,e⬘p⬘ = ␦e,e⬘␦ p,p⬘ e 2 p . 共14兲
冉 p2
2m
冊
− V Lp = E⬘pLp , 共22兲
2mc
which has the form of the Schrödinger equation for a particle
The definition of matrix M in Eq. 共14兲 allows one to write in a repulsive potential. This is the only component that re-
the propagator as mains at the order c0. As a consequence, consistently to the
P = 共1 + M兲−1P共0兲 . 共15兲 order c−2,
冋 册
magnetic term of magnetic properties. Expansion of P in
terms of 1 / c requires the linearization of the inverse matrix x2 −x
as M is of order 1 / c2, and the proper definitions of the elec- Pp = , 共25兲
− x 1 − x2
tronic and positronic manifolds in the one-particle state
space. This was the way followed in previous work.6 In the where
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084102-4 Zaccari et al. J. Chem. Phys. 130, 084102 共2009兲
冤 冥
x2
冤 冥
1− −x 0 0
2
U= 共27兲 1 + M共e兲 = 1 . 共31兲
x2 0 1+ 共E⬘1 + H+兲
x 1− 2mc2 e
2
The corresponding inverse is defined only for the lower 2
is unitary and has the properties ⫻ 2 block, as needed. It is readily obtained as
冋 册
1 0
冤 冥
U U† = Pe , 共28兲 0 0
冉 冊
0 0
共1 + M共e兲兲−1 = 1 −1
. 共32兲
冋 册
0 1+ 共E⬘1 + H+兲
0 0 2mc2 e
U U† = P p , 共29兲
0 1 As mentioned above, in this representation electronic
i.e., this transformation yields a representation such that elec- states are described by the corresponding Pauli spinor. In
tronic states have nonzero amplitude only in the first two order to evaluate the matrix element of Eq. 共8兲 the magnetic
components of the corresponding 4-spinor. In fact, this am- interaction operator must be transformed to this representa-
tion:
plitude is described by the Pauli two-component spinor ˜ e:
冋册 冋册
Le
Se
=U·
˜e
0
. 共30兲
共␣ · A兲T = U† · ␣ · A · U.
x2 where
R=1− . 共35兲
2 1
Eb,NR = 兺 具e兩A2兩e典,
2mc2 eocc
共40兲
For the sake of brevity we define
共␣ · A兲T = 冋 a1
a2
a2
− a1
. 册 共37兲 Eb,P =
1
兺 具e兩A
2mc2 eocc
冉冉 1+
1
共E⬘1 + H+兲
2mc2 e
冊 −1
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084102-5 Geometric ESC approach of magnetic properties J. Chem. Phys. 130, 084102 共2009兲
冉 冊冉 冊
pansion of the magnetic operators a1 and a2, Eq. 共36兲, and on
the molecular ground state 共second term of Eq. 共41兲. These p2 p2
· AH− + H+ · A = · A +V + −V ·A
corrections keep the form of previous work. Eb,P, on the 2m 2m
other hand, contains relativistic corrections strictly originated
in the e-p propagator, which are added up as a geometric
series in the present work.
再
= · A,
p2
2m
冎 共50兲
The expression of Eb, Eq. 共38兲, is consistent to the order since V and · A commute. 兵 ,其 stands for the anticommuta-
−2
c . The effect of the positronic manifold is wholly taken tor. The explicit dependence on the energy eigenvalue Ee⬘ has
into account in this expression by means of operator H+. This been eliminated and the whole contribution can be expressed
procedure sums the linear correction of previous work as a as an expectation value. The full result is
geometric series and therefore it will be referred to as the
1 1
geometric ESC approximation 共GESC兲. The lowest order ap- Eb = 兺 具e兩A2兩e典 + 2mc2 E共2兲共Hmv + HDw ;A2兲
2mc2 e
proximation is obtained by setting R = 1, neglecting the term
of order c−2 in the denominator, and replacing the Pauli 1
spinors by the Schrödinger ones. The nonrelativistic diamag- + 兺 具e兩a22 − A2兩e典 − 具e兩A2x2
2mc2 e
netic term of magnetic properties is thus obtained. In the
relativistic result, it is seen that a different operator is defined + · Ax2 · A兩e典. 共51兲
for each electronic state. However, this dependence is only
−2
through the corresponding orbital energy. It can be taken out Consistently to the order c and taking into account that
from the operator either by neglecting its value, as in the x2 and A2 can be commuted in the expectation value, the last
ZORA,10–12 or by linearizing its contribution, leaving a two term contributions can be rewritten as the expectation
unique operator for the positronic contribution for all elec- value for the operator:
tronic states. The full linearization of the operator yields the 1
diamagnetic term of previous work,6 as it will be explicitly Odiam,LR = − 共兵A2,x2其 + 2 · Ax2 · A + 共x · A兲2
2mc2
shown in Sec. II A. It is worthy to note that from the com-
putational point of view, in order to evaluate the diamagnetic + 共 · Ax兲2兲, 共52兲
term of Eq. 共42兲, the matrix representation of p2 / 2m and V
which is exactly the expression found within the LRESC
are required, which are readily included as part of any
approximation of previous work for the relativistic correction
quantum chemistry program. Therefore, there is nearly no
of the diamagnetic contribution to magnetic properties.6,37
need of extra computational effort to carry out numerical
calculations.
B. The electron-positron contribution to the nuclear
magnetic shielding tensor
A. Linearization and LRESC expression Relativistic effects gathered in Eb,A are equivalent to
of the diamagnetic contribution
those calculated in previous work. The corresponding ex-
The leading order of the relativistic correction to the pressions for the specific case of the nuclear magnetic shield-
diamagnetic contribution is now obtained by linearizing the ing tensor are considered in this section. The nuclear mag-
propagator Eq. 共38兲 to obtain netic shielding tensor of nucleus M can be obtained as
Eb = 兺
e
1 ˜
2mc2
冉
具e兩a2 1 −
1
2mc2
冊
共Ee1 + H+兲 a2兩
˜ e典. 共46兲 共M兲i,j =
2E
=0,B=0 ,
M,i B j M
共53兲
Due to the factor 1 / 共2mc2兲2, the last term must be evaluated where E is the molecular energy in the presence of the mag-
for the nonrelativistic 共i.e., Schrödinger兲 electronic state e netic fields of the nucleus and the uniform external field B0.
and the nonrelativistic approximation for a2: For a point dipole nucleus M:
a共0兲 M ⫻ r M
2 = · A. 共47兲 AM = , 共54兲
r3M
Therefore, the expectation value for each electronic state in
the last term has the form and for the external magnetic field B0:
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084102-6 Zaccari et al. J. Chem. Phys. 130, 084102 共2009兲
AB = 21 B0 ⫻ r. 共55兲 operator H+ were also defined on the basis of the Fock op-
erator F in the following way:
In what follows, the gauge origin is placed at the nucleus
position, i.e., r M = r. The explicit derivation of the final form H+ = T − VF = 2T − F, 共60兲
of the operators involved in Eb,A and LRESC Eb,P was car- where T is the kinetic energy operator and VF stands for the
ried out in Ref. 6. A brief account is presented in the Appen- Hartree–Fock potential. The corresponding matrix elements
dix. The following is obtained: are obtained from the SYSMO program files. Once the matrix
1 20 representation of the inverse propagator of Eq. 共59兲 is ob-
Eb,A = − 兺 具e兩 3 共B0 · M兲␦共rM兲
8m3c4 eocc
tained, the calculation of Eb,P is carried out by inserting the
matrix representations of the nuclear magnetic potential op-
+4 冉 M · L
r3
冊
共B0 · L兲 + B0 · B M,dip兩e典
erator and the uniform magnetic field potential operator,
which are included in the SYSMO program. For comparison
purposes, the linearized LRESC propagator is obtained with
1 共2兲 mv the same procedure, i.e., as the matrix products of the linear-
+ E 共H + HDw ;A M · AB兲, 共56兲
mc2 ized propagator and magnetic field operators. The calculated
values can be splitted into individual MO contributions, al-
Eb,P,LRESC = −
1
冉
8
兺 具e兩 3 共B0 · M兲␦共rM兲
8m3c4 eocc
lowing interesting insight into the obtained values. The non-
relativistic diamagnetic contribution is also obtained with the
nonrelativistic propagator P共0兲, Eq. 共13兲, and the same mag-
冊
+ + 4共AM · AB兲p2 + B0 · BM,dip 兩e典, 共57兲
netic field operators. It is worthy to observe that both at the
relativistic and nonrelativistic levels, it is necessary to en-
large the atomic basis set with higher angular momentum
where basis functions in order to obtain appropriate matrix repre-
3共M · rM兲rM − Mr2M sentations of the vector operators involved.
BM,dip = 共58兲
r5M
is the dipole component of the nucleus magnetic field. IV. RESULTS AND DISCUSSION
Within the formalism developed in the present work, the ex- In order to carry out numerical calculations the noble gas
pression of Eb,P is given by atoms Kr and Xe and the hydrogen halide IH were taken as
Eb,P =
1 ⫻r
兺 具e兩 Mr3
2c2 eocc
冉 冊 model compounds. The main reason for this choice is the
existence of a large amount of benchmark numerical results
冉冉 冊 冊冉 冊
for these systems in the current bibliography. The basis sets
−1
1 B0 used in the calculations are based on Faegri’s basis sets46 for
⫻ 1+ 共E⬘1 + H+兲 −1 ⫻ r 兩e典.
2mc2 e 2 Kr and Xe and aug-ccpVTZ basis47–49 for I, enlarged in dif-
ferent ways until saturation of results was achieved. On one
共59兲
hand, tight functions were added in order to have flexibility
The corresponding contributions to the magnetic shield- in the vicinity of the heavy nucleus. On the other, higher
ing tensor M obtained according to Eq. 共53兲 will be referred angular momentum basis functions were added in order to be
to as b,A and b,P, respectively. able to reproduce the action of the vector operators involved
in Eq. 共59兲. In the latter case, it was verified that the nonrel-
ativistic value obtained with Eq. 共59兲 in the limit c → ⬁ is
III. METHOD OF CALCULATION coincident with the result of the diamagnetic operator. The
final results make use of uncontracted basis sets of quality:
In order to carry out numerical calculations of the e-p 共17s24p18d8f兲 for Kr, 共22s21p15d15f兲 for Xe,
contribution to the nuclear magnetic shielding tensor with 共23s18p13d13f兲 for I, and 共6s4p3d兲 for H.
the formalism of the previous section the following proce- Results for the noble gas atoms Kr and Xe are presented
dure was adopted. Contributions contained in Eb,A involve in Tables I and II, respectively. Values obtained with the
operators for which explicit numerical results were obtained formalism developed in the present work are indicated as
in previous works,7–9,43 both with the DALTON 共Ref. 44兲 and “GESC” to indicate that the geometric approximation of the
SYSMO 共Ref. 45兲 programs. In order to calculate the newly propagator is used. Values of the LRESC approach are also
developed term Eb,P a computational program was imple- quoted for comparison. Contributions from individual con-
mented which works as a subroutine of the SYSMO program. verged occupied orbitals are listed. As it was shown in pre-
The matrix representation of the inverse propagator of Eq. vious work,50 the total relativistic effect is defined to a large
共59兲 is carried out in the molecular orbital 共MO兲 basis set of extent by contributions from the inner shell s-type orbitals. It
a Hartree–Fock calculation. The eigenvalue of the electronic is seen that for these contributions the GESC and linearized
state E⬘ of each term of Eq. 共59兲 is replaced by the corre- LRESC values differ significantly. As a consequence, contri-
sponding orbital energy of the involved MO. This is consis- bution b,P to the relativistic effect on e-p rotations is re-
tent with taking the Fock operator as the one-body Hamil- duced in absolute value by a factor of nearly 2 in both Kr and
tonian of the problem. Consistently, the matrix elements of Xe. The difference between both approaches becomes less
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084102-7 Geometric ESC approach of magnetic properties J. Chem. Phys. 130, 084102 共2009兲
TABLE I. Atomic orbital contributions to relativistic effects on the nuclear and previous Breit–Pauli and LRESC two-component results
magnetic shielding constant of Kr for the isolated atom arising from e-p of the bibliography. In order to obtain the full e-p values of
rotations given by Eq. 共59兲. LRESC, GESC, and difference between both.
Values in ppm.
Table III, the contributions arising from Eb,A, Eq. 共56兲, must
be computed. As it is shown in the Appendix, the corre-
b,P sponding values can be obtained by adequate rescaling of
numerical data taken from Refs. 7 and 43 or Refs. 8 and 9. It
AO NR GESC LRESC Difference
is seen that the GESC result comes much closer to the four-
1s 1260.13 ⫺121.27 ⫺208.73 87.45 component ones than the LRESC/BPPT values in all cases.
2s 281.11 ⫺13.64 ⫺23.91 10.27 The differences in the cases of Xe and I are within 1% of the
2P 共⫻3兲 279.32 ⫺3.09 ⫺3.21 0.12 total absolute shielding.
3s 93.63 ⫺2.28 ⫺3.09 1.62
3p 共⫻3兲 89.56 ⫺0.53 ⫺0.54 0.02
3d 共⫻5兲 80.83 ⫺0.17 ⫺0.17 0.001 V. CONCLUDING REMARKS
4s 28.55 ⫺0.24 ⫺0.83 0.59
An alternative approach for the calculation of the e-p
4p 共⫻3兲 23.29 ⫺0.04 0.07 ⫺0.11
contribution to magnetic properties within the LRESC
Total 3244.08 ⫺149.26 ⫺249.28 100.02
scheme was developed. Its main features are as follows. The
ESC approximation is applied to the inverse propagator ma-
important as orbitals with zero density at the nucleus are trix in such a way that the relativistic effect is now summed
considered. It is worthy to note a significant difference in the up as a geometric series. However, no explicit evaluation of
stability and reliability of results of the GESC and LRESC positronic states is needed and the final form is expressed in
calculated values as obtained in the present work. As the terms of Breit–Pauli spinors corresponding to electronic
basis set is enlarged with tight s-type functions, the linear- states only. Due to the presence of operator H+ in the de-
ized propagator shows numerical problems, which are due to nominator, a singularity in the vicinity of the nucleus is
the 1 / r dependence of H+. This difficulty is only overcome avoided, yielding a better description of the sought relativis-
when the operator form of Eq. 共52兲 based in the elimination tic effect. This feature has a deep influence in numerical
of the potential V in Eq. 共50兲 is considered. On the contrary, results of the nuclear magnetic shielding tensor, especially on
in the GESC expressions, inclusion of tight s functions does those contributions corresponding to inner shell tight orbit-
not have a significant influence in the propagator matrix, as als. In fact, numerical results presented in this work show
in this case the large effect of the 1 / r dependence is in the that with the GESC approximation, the inner shell s-type
denominator. This is a situation in which the linearization in orbitals yield a smaller contribution in absolute value as
terms of c−2 yields an operator expression which is singular compared to the LRESC scheme. As a consequence, the total
in the vicinity of the nucleus. This singularity is spurious and nuclear shielding of the heavy nucleus is in close agreement
does not correspond to a good description of the relativistic with results of four-component approaches for atomic num-
effect. The GESC propagator overcomes this problem in a bers of the order Z = 50, i.e., in the fifth row of the Periodic
way similar to that of the ZORA10–12 approach. Table.
In Table III the total e-p contribution and the total abso-
lute value of the relativistic nuclear magnetic shielding con- ACKNOWLEDGMENTS
stants of the isolated Kr and Xe atoms and of I in IH ob-
Financial support from the University of Buenos Aires
tained in the present work are compared to four-component
共Grant No. UBACYT X222兲 and CONICET 共Grant No.
PIP5119兲 is gratefully acknowledged.
TABLE II. Atomic orbital contributions to relativistic effects on the nuclear
magnetic shielding constant of Xe for the isolated atom arising from e-p
rotations given by Eq. 共59兲. LRESC, GESC, and difference between both. APPENDIX: EXPLICIT FORM OF LRESC OPERATORS
Values in ppm. FOR THE E-P CONTRIBUTION TO THE
MAGNETIC SHIELDING TENSOR
b,P
The first term of Eq. 共56兲 is worked out as follows:6,37
AO NR GESC LRESC Difference
1
1s 1898.06 ⫺324.70 ⫺618.91 294.20 Eb,A
1 = 兺 具e兩a22 − A2兩e典
2c2 eocc
2s 436.98 ⫺39.39 ⫺63.39 24.01
2p 共⫻3兲 436.28 ⫺11.06 ⫺12.10 1.03
1
3s
3p 共⫻3兲
160.71
157.76
⫺8.24
⫺2.48
⫺16.80
⫺2.71
8.56
0.24
= 兺 具e兩共N共 . A兲N − x共 . A兲x兲2 − A2兩e典
2c2 eocc
3d 共⫻5兲 152.80 ⫺1.017 ⫺1.035 0.017
−1 1
4s
4p 共⫻3兲
65.41
61.82
⫺1.75
⫺0.504
⫺5.23
⫺0.546
3.48
0.042
= 兺 具e兩 2 p2A2 + Ap2A + 共 · A · p兲2
8c4 eocc
4d 共⫻5兲 53.56 ⫺0.170 ⫺0.173 0.003
5s 23.00 ⫺0.218 ⫺0.304 0.086 1 1
+ · Ap2 · A + A2 p2 + 共 · A · p兲2兩e典, 共A1兲
5p 共⫻3兲 19.47 ⫺0.059 ⫺0.026 ⫺0.033 2 2
Total 5641.98 ⫺422.56 ⫺756.82 334.27
where x and N were defined in Eqs. 共26兲 and 共35兲 and terms
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084102-8 Zaccari et al. J. Chem. Phys. 130, 084102 共2009兲
TABLE III. Comparison of e-p contributions and total values of the nuclear magnetic shielding constant of Kr, Xe, and I obtained with present work GESC
formalism, LRESC, and four-component methods. Values in ppm.
Nucleus Kr Xe I
of order higher than c−4 have been neglected. The following 具e兩2共iAN,j兲共iAB,j兲兩e典 = 具e兩B0 · BN兩e典, 共A8兲
relations hold:
具e兩p2A2兩e典 = 具e兩A2 p2兩e典 共A2兲 具e兩 − ABⵜ2AN兩e典 = 4具e兩AB · 共ⵜ ⫻ ␦共rN兲兲兩e典,
冉 冊
Considering a singlet ground state wave function and
therefore neglecting spin-dependent operators, Eq. 共A1兲 can 1 · LN
Eb,A
1 =− 4 兺 具e兩4 共B0 · L兲 + B0 · BN,dip
be re-expressed as 8c eocc r3n
1 20
Eb,A
1 =− 兺 具e兩4共p · A兲2 + B2 − 共pA2兲 · p兩e典, 共A6兲
8c4 eocc
+
3
· B0␦共r兲兩e典. 共A12兲
具e兩共pA2兲 · p兩e典 = 21 具e兩ⵜ2A2兩e典 The Eb,P,LRESC contribution contains the following matrix el-
ements:
= 具e兩共A · ⵜ2A兲 + 共iA j兲共iA j兲兩e典,
具e兩共 · A兲共共 · A兲p2 + p2共 · A兲兲兩e典
共A7兲
= 具e兩A2 p2 + Ap2 · A兩e典, 共A13兲
where i , j stand for Cartesian components and Einstein’s
convention of sum of repeated indices is applied. where only spin-independent operators are retained as a sin-
Inserting the magnetic potentials of the uniform and glet ground state wave function is assumed. Since
nucleus fields and retaining terms bilinear in and B0 the
following is obtained: p2A = 共p2A兲 + 2共piA兲pi + Ap2 , 共A14兲
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084102-9 Geometric ESC approach of magnetic properties J. Chem. Phys. 130, 084102 共2009兲
冉 冊
Chem. Phys. 124, 054103 共2006兲.
1 · LN 38
R. E. Moss, Advanced Molecular Quantum Mechanics 共Chapman and
EL-PSO = − 4 兺 具e兩4 共B0 · L兲兩e典, 共A21兲 Hall, London, 1973兲.
2c eocc r3n 39
C. Cohen-Tannoudji, J. Dupont-Roc, and G. Grynberg, Photons and At-
oms 共Wiley, New York, 1997兲.
40
1 F. Gross, Relativistic Quantum Mechanics and Field Theory 共Wiley, New
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