We present the results of an extended study of five birefringences—Kerr, Cotton–Mouton, Buckingham, Jones, and Magnetoelectric—on benzene in the gas phase. The relevant molecular quantities—first-order properties, linear, quadratic, and cubic response functions—are computed employing the density-functional theory (DFT) response theory, with a choice of functionals. In some cases, different functionals are employed for the wave-function computational step and for the subsequent analytical response calculation to determine the combination yielding at the same time the optimal energy and energy derivative results. Augmented correlation consistent basis sets of double and triple zeta quality are used. The DFT results are compared to those obtained at the Hartree–Fock level and in some cases within a coupled cluster singles and doubles electronic structure model. The study tries to assess the ability of the DFT response theory to describe a wide range of properties in a system of rather large size and high complexity. The relative strength of the five birefringences for plausible experimental conditions is determined and, when possible, comparison is made with the results of the measurements.

1.
C. J. F. Böttcher and P. Bordewijk, Theory of Electric Polarization: Dielectric in Time-Dependent Fields (Elsevier, Amsterdam, 1978), Vol. 2.
2.
L. D. Barron, Molecular Light Scattering and Optical Activity (Cambridge University Press, Cambridge, 1982).
3.
G. H. Wagnière, Linear and Nonlinear Optical Properties of Molecules (Verlag Helvetica Chimica Acta, Basel, 1993).
4.
J. Michl and E. W. Thulstrup, Spectroscopy with Polarized Light (Wiley, New York, 1995).
5.
N. Bloembergen, Nonlinear Optics, 4th ed. (World Scientific, Singapore, 1996).
6.
A. Hinchliffe and R. W. Munn, Molecular Magnetism (Wiley, Chichester, 1985).
7.
T. Helgaker, P. Jørgensen, and J. Olsen, Molecular Electronic-Structure Theory (Wiley, Chichester, 1999).
8.
J.
Olsen
and
P.
Jørgensen
,
J. Chem. Phys.
82
,
3235
(
1985
).
9.
J. Olsen and P. Jørgensen, in Modern Electronic Structure Theory Part II, edited by D. R. Yarkony (World Scientific, Singapore, 1995), p. 857.
10.
T.
Helgaker
,
P. J.
Wilson
,
R. D.
Amos
, and
N. C.
Handy
,
J. Chem. Phys.
113
,
2088
(
2000
).
11.
P.
Sałek
,
O.
Vahtras
,
T.
Helgaker
, and
H.
Ågren
,
J. Chem. Phys.
117
,
9630
(
2002
).
12.
A.
Cotton
and
H.
Mouton
,
C. R. Acad. Sci. III
141
,
317
(
1905
).
13.
A. D.
Buckingham
and
J. A.
Pople
,
Proc. Phys. Soc. London, Sect. B
69
,
1133
(
1956
).
14.
D.
Jonsson
,
P.
Norman
,
H.
Ågren
,
A.
Rizzo
,
S.
Coriani
, and
K.
Ruud
,
J. Chem. Phys.
114
,
8372
(
2001
).
15.
C.
Cappelli
,
B.
Mennucci
,
J.
Tomasi
,
R.
Cammi
, and
A.
Rizzo
,
Chem. Phys. Lett.
346
,
251
(
2001
).
16.
A.
Rizzo
,
K.
Ruud
, and
D. M.
Bishop
,
Mol. Phys.
100
,
799
(
2002
).
17.
Y.
Luo
,
D.
Jonsson
,
P.
Norman
et al.,
Int. J. Quantum Chem.
70
,
219
(
1998
).
18.
C.
Cappelli
,
B.
Mennucci
,
J.
Tomasi
,
R.
Cammi
,
A.
Rizzo
,
G.
Rikken
,
R.
Mathevet
, and
C.
Rizzo
,
J. Chem. Phys.
118
,
10712
(
2003
).
19.
C.
Rizzo
,
A.
Rizzo
, and
D. M.
Bishop
,
Int. Rev. Phys. Chem.
16
,
81
(
1997
).
20.
A. D.
Buckingham
,
J. Chem. Phys.
30
,
1580
(
1959
).
21.
A. D.
Buckingham
and
R. L.
Disch
,
Proc. R. Soc. London, Ser. A
273
,
275
(
1963
).
22.
S.
Coriani
,
A.
Halkier
,
D.
Jonsson
,
J.
Gauss
,
A.
Rizzo
, and
O.
Christiansen
,
J. Chem. Phys.
118
,
7329
(
2003
).
23.
D.
Marchesan
,
S.
Coriani
, and
A.
Rizzo
,
Mol. Phys.
101
,
1851
(
2003
).
24.
C. Cappelli, U. Ekström, A. Rizzo, and S. Coriani, J. Comput. Methods Sci. Eng. (in press).
25.
S. Coriani, A. Halkier, and A. Rizzo, in Recent Research Developments in Chemical Physics, edited by G. Pandalai (Transworld Scientific, Kerala, India, 2001), Vol. 2, p. 1.
26.
A. D.
Buckingham
and
H. C.
Longuet-Higgins
,
Mol. Phys.
14
,
63
(
1968
).
27.
D. A.
Imrie
and
R. E.
Raab
,
Mol. Phys.
74
,
833
(
1991
).
28.
R. E.
Raab
and
O. L.
de Lange
,
Mol. Phys.
101
,
3467
(
2003
).
29.
O. L.
de Lange
and
R. E.
Raab
,
Mol. Phys.
102
,
125
(
2004
).
30.
R. C.
Jones
,
J. Opt. Soc. Am.
38
,
671
(
1948
).
31.
E. B.
Graham
and
R. E.
Raab
,
Proc. R. Soc. London, Ser. A
390
,
73
(
1983
).
32.
F.
Pockels
,
Radium
10
,
152
(
1913
).
33.
E. B.
Graham
and
R. E.
Raab
,
Mol. Phys.
52
,
1241
(
1984
).
34.
A.
Rizzo
and
S.
Coriani
,
J. Chem. Phys.
119
,
11064
(
2003
).
35.
J.
Kerr
,
Philos. Mag.
50
,
337
(
1875
).
36.
C.
Hättig
,
J. L.
Cacheiro
,
B.
Fernández
, and
A.
Rizzo
,
Mol. Phys.
101
,
1983
(
2003
).
37.
S.
Coriani
,
C.
Hättig
,
P.
Jørgensen
, and
T.
Helgaker
,
J. Chem. Phys.
113
,
3561
(
2000
).
38.
S.
Coriani
,
P.
Jørgensen
,
O.
Christiansen
, and
J.
Gauss
,
Chem. Phys. Lett.
330
,
463
(
2000
).
39.
S.
Coriani
,
C.
Hättig
, and
A.
Rizzo
,
J. Chem. Phys.
111
,
7828
(
1999
).
40.
S.
Coriani
,
M.
Pecul
,
A.
Rizzo
,
P.
Jørgensen
, and
M.
Jaszuński
,
J. Chem. Phys.
117
,
6417
(
2002
).
41.
S. J. A.
van Gisbergen
,
V. P.
Osinga
,
O. V.
Gritsenko
,
R.
van Leeuwen
,
J. G.
Snijders
, and
E. J.
Baerends
,
J. Chem. Phys.
105
,
3142
(
1996
).
42.
S. H.
Vosko
,
L.
Wilk
, and
M.
Nusair
,
Can. J. Phys.
58
,
1200
(
1980
).
43.
C.
Lee
,
W.
Yang
, and
R. G.
Parr
,
Phys. Rev. B
37
,
785
(
1988
).
44.
A. D.
Becke
,
Phys. Rev. A
38
,
3098
(
1988
).
45.
B.
Miehlich
,
A.
Savin
,
H.
Stoll
, and
H.
Preuss
,
Chem. Phys. Lett.
157
,
200
(
1989
).
46.
A. D.
Becke
,
J. Chem. Phys.
98
,
5648
(
1993
).
47.
A. D.
Becke
,
Phys. Rev. A
38
,
3098
(
1988
).
48.
G. L. D.
Ritchie
and
J. N.
Watson
,
Chem. Phys. Lett.
322
,
143
(
2000
).
49.
A. D.
Buckingham
,
Proc. Phys. Soc., London, Sect. A
68
,
910
(
1955
).
50.
A. D.
Buckingham
,
Proc. R. Soc. London, Ser. A
267
,
271
(
1962
).
51.
A. D.
Buckingham
and
M. J.
Jamieson
,
Mol. Phys.
22
,
117
(
1971
).
52.
S.
Coriani
,
C.
Hättig
,
P.
Jørgensen
,
A.
Rizzo
, and
K.
Ruud
,
J. Chem. Phys.
109
,
7176
(
1998
).
53.
A.
Rizzo
,
S.
Coriani
,
A.
Halkier
, and
C.
Hättig
,
J. Chem. Phys.
113
,
3077
(
2000
).
54.
B. Jansı́k, P. Sałek, D. Jonsson, O. Vahtras, and H. Ågren, J. Chem. Phys. (submitted).
55.
B. Jansı́k, Ph.D. thesis, KTH Biotechnology, (2004).
56.
E.
Gross
and
W.
Kohn
,
Adv. Quantum Chem.
21
,
255
(
1990
).
57.
S. J. A.
van Gisbergen
,
J. G.
Snijders
, and
E. J.
Baerends
,
J. Chem. Phys.
103
,
9347
(
1995
).
58.
R.
van Leeuwen
and
E. J.
Baerends
,
Phys. Rev. A
49
,
2421
(
1994
).
59.
J. P.
Perdew
,
K.
Burke
, and
M.
Ernzerhof
,
Phys. Rev. Lett.
77
,
3865
(
1996
).
60.
J. P.
Perdew
,
K.
Burke
, and
M.
Ernzerhof
,
Phys. Rev. Lett.
78
,
1396
(
1997
).
61.
T. Helgaker, H. J. A. Jensen, P. Jørgensen et al., DALTON, an ab initio electronic structure program, Release 1.2 2001, see //www.kjemi.uio.no/software/dalton/dalton.html.
62.
D. E.
Woon
and
T. H.
Dunning
, Jr.
,
J. Chem. Phys.
98
,
1358
(
1993
).
63.
D. E.
Woon
and
T. H.
Dunning
, Jr.
,
J. Chem. Phys.
100
,
2975
(
1994
).
64.
G. H. Herzberg, Electronic Spectra and Electronic Structure of Polyatomic Molecules, Molecular Spectra and Molecular Structure III (Van Nostrand Reinhold, Princeton, 1966).
65.
I. Mills, T. Cvitaš, K. Homann, N. Kallay, and K. Kuchitsu, IUPAC, Physical Chemistry Division: Quantities, Units, and Symbols in Physical Chemistry (Blackwell Science, Oxford, 1993).
66.
P. J.
Mohr
and
B. N.
Taylor
,
Rev. Mod. Phys.
72
,
351
(
2000
).
67.
M. R.
Battaglia
,
A. D.
Buckingham
, and
J. H.
Williams
,
Chem. Phys. Lett.
78
,
421
(
1981
).
68.
M. P.
Bogaard
,
A. D.
Buckingham
,
R. K.
Pierens
, and
A. H.
White
,
J. Chem. Soc., Faraday Trans. 1
74
,
3008
(
1978
).
69.
I. R.
Gentle
and
G. L. D.
Ritchie
,
J. Phys. Chem.
93
,
7740
(
1989
).
70.
M. E.
Baur
,
D. A.
Horsma
,
C. M.
Knobler
, and
P.
Perez
,
J. Phys. Chem.
73
,
641
(
1969
).
71.
D. M.
Bishop
,
Adv. Chem. Phys.
104
,
1
(
1998
).
72.
O.
Christiansen
,
C.
Hättig
, and
P.
Jørgensen
,
Spectrochim. Acta, Part A
55
,
509
(
1999
).
73.
G. R.
Alms
,
A. W.
Burnham
, and
W. H.
Flygare
,
J. Chem. Phys.
63
,
3321
(
1975
).
74.
A. A. Hasanein, Modern Nonlinear Optics, Advances in Chemical Physics Series, Vol. LXXXV, edited by M. Evans and S. Kielich (Wiley, New York, 1993), Part II, p. 415.
75.
H.
Soscún
,
J.
Hernández
,
R.
Escobar
,
C.
Toro-Mendoza
,
Y.
Alvarado
, and
A.
Hinchliffe
,
Int. J. Quantum Chem.
90
,
497
(
2002
).
76.
T.
Bondo Pedersen
,
A. M. J.
Sánchez de Merás
, and
H.
Koch
,
J. Chem. Phys.
120
,
8887
(
2004
).
77.
I. Garcia
Cuesta
,
T.
Bondo Pedersen
,
H.
Koch
, and
A. M. J.
Sánchez de Merás
,
Chem. Phys. Lett.
390
,
170
(
2004
).
78.
P.
Norman
,
D.
Jonsson
, and
H.
Ågren
,
Chem. Phys. Lett.
268
,
337
(
1997
).
79.
M.
Okruss
,
R.
Müller
, and
A.
Hese
,
J. Chem. Phys.
110
,
10393
(
1999
).
80.
J. H. V. Vleck, The Theory of Electric and Magnetic Susceptibilities (Oxford University Press, Oxford, 1932).
81.
F.
London
,
J. Phys. Radium
8
,
397
(
1937
).
82.
R.
Ditchfield
,
J. Chem. Phys.
56
,
5688
(
1972
).
83.
H. F.
Hameka
,
Mol. Phys.
1
,
203
(
1958
).
84.
H. F.
Hameka
,
Z. Naturforsch. A
14
,
599
(
1959
).
85.
H. F.
Hameka
,
Rev. Mod. Phys.
34
,
87
(
1962
).
86.
K.
Ruud
,
T.
Helgaker
,
K. L.
Bak
,
P.
Jørgensen
, and
H. J. A.
Jensen
,
J. Chem. Phys.
99
,
3847
(
1993
).
87.
A.
Rizzo
,
T.
Helgaker
,
K.
Ruud
,
A.
Barszczewicz
,
M.
Jaszuński
, and
P.
Jørgensen
,
J. Chem. Phys.
102
,
8953
(
1995
).
88.
M. P.
Bogaard
,
A. D.
Buckingham
,
M. G.
Corfield
,
D. A.
Dunmur
, and
A. H.
White
,
Chem. Phys. Lett.
12
,
558
(
1972
).
89.
P. B.
Lukins
,
A. D.
Buckingham
, and
G. L. D.
Ritchie
,
J. Phys. Chem.
88
,
2414
(
1984
).
90.
T. A.
Keith
and
R. F. W.
Bader
,
Chem. Phys. Lett.
194
,
1
(
1992
).
91.
T. A.
Keith
and
R. F. W.
Bader
,
Chem. Phys. Lett.
210
,
223
(
1993
).
92.
M. J. Frisch, G. W. Trucks, H. B. Schlegel et al., GAUSSIAN 03, Revision A1 (GAUSSIAN, Inc., Pittsburgh PA, 2003).
93.
R. J.
Doerksen
and
A. J.
Thakkar
,
J. Phys. Chem. A
103
,
10009
(
1999
).
94.
K.
Hald
,
A.
Halkier
,
P.
Jørgensen
, and
S.
Coriani
,
J. Chem. Phys.
117
,
9983
(
2002
).
95.
M. P.
Bogaard
,
B. J.
Orr
,
A. D.
Buckingham
, and
G. L. D.
Ritchie
,
Mol. Phys.
18
,
575
(
1970
).
96.
A. D. Buckingham, in Molecular Electro-Optics, edited by C. O’Konski (Dekker, New York, 1976).
97.
S. M.
Cybulski
and
D. M.
Bishop
,
J. Chem. Phys.
101
,
424
(
1994
).
98.
H.
Geschka
,
S.
Pferrer
,
H.
Häussler
, and
W.
Hüttner
,
Ber. Bunsenges. Phys. Chem.
86
,
790
(
1982
).
99.
J. D.
Augspurger
and
C. E.
Dykstra
,
Mol. Phys.
76
,
229
(
1992
).
100.
J.
Vrbancich
and
G. L. D.
Ritchie
,
J. Chem. Soc., Faraday Trans. 2
76
,
648
(
1980
).
101.
M. H.
Coonan
and
G. L. D.
Ritchie
,
Chem. Phys. Lett.
293
,
197
(
1998
).
102.
G. L. J. A.
Rikken
,
E.
Raupach
, and
T.
Roth
,
Physica A
294–295
,
1
(
2001
).
103.
T.
Roth
and
G. L. J. A.
Rikken
,
Phys. Rev. Lett.
85
,
4478
(
2000
).
104.
T. Roth, M.S. thesis, Darmstadt University of Technology and Grenoble High Magnetic-Field Laboratory, 2000.
105.
G. L. D. Ritchie, in Optical, Electric, and Magnetic Properties of Molecules, edited by D. C. Clary and B. Orr (Elsevier, Amsterdam, The Netherlands, 1997), p. 67.
106.
C. G. Le Févre and R. J. W. Le Févre, in Physical Methods of Chemistry, edited by A. Weissberger and B. W. Rossiter (Wiley-Interscience, New York, 1972), Part III C, p. 399.
107.
Handbook of Chemistry and Physics, 57th ed., edited by R. C. West (CRC, Cleveland, Ohio, 1977).
This content is only available via PDF.
You do not currently have access to this content.