ANALYSIS OF ELECTRONIC-TRANSITIONS AS THE DIFFERENCE OF ELECTRON-ATTACHMENT AND DETACHMENT DENSITIES
ANALYSIS OF ELECTRONIC-TRANSITIONS AS THE DIFFERENCE OF ELECTRON-ATTACHMENT AND DETACHMENT DENSITIES
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DOI：
10.1021/j100039a012
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发表时间：
1995-09-28
影响因子：
--
通讯作者：
WHITE, CA
中科院分区：
文献类型：
--
作者：
HEADGORDON, M;GRANA, AM;WHITE, CA
提出了一种分析分子垂直电子跃迁计算的新方法。两个态之间的单电子差密度矩阵被分解为描述电荷从初始状态移除的‘’脱离密度‘’的负数加上描述其在激发态中的新排列的‘’附着‘’密度的负值。这种方法与激发态从占据轨道到非占据轨道的电子促进的简单图景密切相关，但它可以应用于任意复杂的波函数。附着和脱离密度的轨迹是在跃迁中促进的电子数量的量度。计算和分析了甲醛和硝甲基自由基中电子跃迁的附着和脱附密度。
A new method for analyzing calculations of vertical electronic transitions in molecules is proposed. The one-electron difference density matrix between the two states is decomposed into the negative of a ''detachment density'' describing removal of charge from the initial state plus an ''attachment'' density describing its new arrangement in the excited state. This approach relates closely to the simple picture of excited states as electron promotions from occupied to unoccupied orbitals, and yet it can be applied to arbitrarily complex wave functions. The trace of the attachment and detachment densities is a measure of the number of electrons promoted in a transition. Attachment and detachment densities are calculated and analyzed for electronic transitions in formaldehyde and the nitromethyl radical.