采用量子化学方法计算分析了阴离子自由基TCNQ-及其铜盐CuTCNQ单体、二聚体的非线性光学(NLO)性质.结果表明,将Cu+引入TCNQ-分子,极化率值减小,Cu+的位置不同对分子NLO系数的贡献不同;二聚体分子的极化率与其结合能相关,同时分子的几何构型影响二阶NLO系数.由前线分子轨道组成得到,电子在前线分子轨道间跃迁产生的电荷转移程度决定分子三阶NLO系数的大小,二聚体分子前线分子轨道在两共轭平面间的相互重叠对分子的三阶NLO系数有一定贡献. The nonlinear optical (NLO) properties of monomeric and dimeric anion TCNQ- and its copper salt CuTCNQ were calculated by quantum chemical method. The results showed that the introduction of Cu + into TCNQ- The contributions of dimeric molecules are related to their binding energies, and the geometrical configurations of the molecules affect the second-order NLO coefficients, which are composed of the frontier molecular orbital, the electron transition in the frontier molecular orbital The degree of charge transfer produced determines the size of the third-order NLO coefficient of the molecule, and the overlap of the front molecular orbital of the dimer molecules in the conjugate planes contributes to the third-order NLO coefficient of the molecule.