Time-dependent Hartree-Fock theory has been used to study the electronic optical response of a series of linear polyene cations(+1 and +2)in strong laser fields.The interaction of ethylene,butadiene,and hexatriene,with pulsed and CW fields corresponding to 8.75 x 10~(13)W/cm~2 and 760 nm,have been calculated using the 6-31G(d,p)basis set.Nonadiabatic processes including nonlinear response of the dipole moment to the field and nonresonsnat energy deposition into excited states were more pronounced for the monocations in comparison with dications.For a given charge state and geometry,the nonadiabatic effects in the charge distribution and instantaneous dipole increased with the length of the polyene.For pulsed fields,the instantaneous dipole continued to oscillate after the field returned to zero and corresponded to a nonresonant electronic excitation involving primarily the lowest electronic transition.For a given molecule and fixed charge state,the degree of nonadiabatic coupling and excitation was greater for geometries with lower excitation energies.
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机译：时变哈特里-福克理论被用来研究一系列线性多烯阳离子（+1和+2）在强激光场中的电子光学响应。乙烯，丁二烯和己三烯与脉冲场和连续波场的相互作用使用6-31G（d，p）基集计算出对应于8.75 x 10〜（13）W / cm〜2和760 nm的纳米绝热过程，包括偶极矩对磁场的非线性响应和非共振能量沉积与指示剂相比，单阳离子更容易进入激发态。对于给定的电荷态和几何形状，电荷分布和瞬时偶极子的非绝热效应随着多烯长度的增加而增加。对于脉冲场，瞬时偶极子继续振荡在电场恢复为零并对应于主要涉及最低电子跃迁的非共振电子激发之后。对于给定的分子和固定电荷状态，非绝热耦合度和e对于具有较低激发能的几何形状，x激发更大。
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