Electron Correlation Effects on the Longitudinal Polarizabilities and Second Hyperpolarizabilities of Polyenes: A Finite Field Study

Table 1

Longitudinal polarizabilities per unit cell 𝛼_𝐿/𝑁 of polyenes obtained by various chemical models (in a.u., N is the number of unit cells or double bonds in the system).

N	2	3	4	5	6	7	8	9	10
6-31G
HF	40.0	48.7	58.8	68.1	76.5	84.1	90.7	96.6
MP2	32.5	39.9	47.4	54.3	60.5	66.0	70.9	75.1
CCSD	31.7	37.3	43.0	47.9	52.0	55.4	58.2	60.6
SVWN	37.2	50.4	65.1	80.8	97.0	114	130	147	163
BLYP	37.3	50.6	65.3	81.0	97.1	114	130	147	163
B3LYP	37.4	49.3	62.4	75.8	89.2	102	115	127	138
6-31G(d)
HF	39.4	48.4	58.4	67.7	76.1	83.5	90.1
MP2	33.5	42.0	50.6	58.7	66.1	72.8	78.7
CCSD	33.4	40.4	47.5	53.7	59.2	63.8	67.8
SVWN	37.4	51.1	66.0	82.0	98.6	116	133	150	167
BLYP	37.5	51.2	66.1	82.0	98.5	115	132	149	166
B3LYP	37.5	49.8	63.1	76.8	90.4	104	117	129	141
6-31+G
HF	43.7	52.6	62.8	72.2	80.7	88.3	94.9	101
MP2	36.8	44.5	52.3	59.5	65.9	71.7	76.7	81.1
CCSD	35.4	41.2	47.1	52.2	56.5	60.1	63.0	65.5
SVWN	41.6	55.3	70.4	86.5	103	120	137	154	171
BLYP	42.4	56.3	71.5	87.6	104	121	138	155	171
B3LYP	41.8	54.2	67.6	81.3	94.9	108	121	133	145
6-31+G(d)
HF	56.4	68.4	81.8	94.1	105	115
MP2	49.3	61.0	72.7	83.6	93.6	103
CCSD	48.5	58.0	67.5	76.0	83.3	89.6
SVWN	41.9	56.1	71.6	87.9	105	122	140	157	174
BLYP	42.7	57.1	72.6	89.0	106	123	140	157	174
B3LYP	42.1	54.9	68.6	82.6	96.5	110	123	135	147