SEMIEMPIRICAL CALCULATIONS OF HYPERPOLARIZABILITIES FOR DONOR-ACCEPTOR MOLECULES - COMPARISON TO EXPERIMENT
SEMIEMPIRICAL CALCULATIONS OF HYPERPOLARIZABILITIES FOR DONOR-ACCEPTOR MOLECULES - COMPARISON TO EXPERIMENT
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DOI：
10.1021/j100194a027
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发表时间：
1992-07-23
影响因子：
--
通讯作者：
DIXON, DA
中科院分区：
文献类型：
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作者：
MATSUZAWA, N;DIXON, DA
采用PM-3参数化MNDO哈密顿量的有限场方法计算了苯、联苯、芴、苯乙烯、芪和二苯乙炔的偶极矩（μ）、极化率（α）、超极化率（β）和二阶超极化率（γ）.这些结果进行了比较，从EFISH和THG测量获得的实验值。获得了良好的相关性，测量值和计算值（计算/测量）之间的系数分别为1.11，0.75，1.00和0.94 μ，α，β和γ。计算一般再现的依赖性的β和γ的强度的供体和受体和增强的β和γ的电荷转移。对于每一类化合物，取代基的计算超极化率的影响进行了研究。的计算值和测量值之间的差异被发现为某些组的取代基。
The dipole moments (mu), polarizabilities (alpha), hyperpolarizabilities (beta), and second-order hyperpolarizabilities (gamma) of benzenes, biphenyls, fluorenes, styrenes, stilbenes, and tolans have been calculated by a finite field method with the PM-3 parametrization of the MNDO Hamiltonian. These results were compared to experimental values obtained from EFISH and THG measurements. Good correlations were obtained, and coefficients between the measured and calculated values (calculated/measured) were 1.11, 0.75, 1.00, and 0.94 for mu, alpha, beta, and gamma, respectively. The calculations generally reproduced the dependence of beta and gamma on the strength of donors and acceptors and the enhancement of beta and gamma by charge transfer. For each class of compounds, the effect of substituents on the calculated hyperpolarizabilities were studied. Differences between the calculated and measured values were found for certain sets of substituents.