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首页> 外文期刊>Chemistry: A European journal >Photodissociation and Electronic Spectroscopy of [Re(H)(CO)_3(H-dab)] (H-dab=1,4-diaza-1,3-butadiene): Quantum Wavepacket Dynamics Based on Ab Initio Potentials
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Photodissociation and Electronic Spectroscopy of [Re(H)(CO)_3(H-dab)] (H-dab=1,4-diaza-1,3-butadiene): Quantum Wavepacket Dynamics Based on Ab Initio Potentials

机译：[Re（H）（CO）_3（H-dab）]（H-dab = 1,4-diaza-1,3-butadiene）的光解离和电子光谱：基于从头算势的量子波包动力学

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摘要

The photodissociatin dynamics of [Re(H)(CO)_3(H-dab)] (H-dab=1,4-diaza-1,3-butadiene) were studied by means of wavepacket propagations on CASSCF/MR-CCI potentials calculaed for the elecronic ground state and low-lying excited states as a function of two coordinates, q_a and Q_b, that correspond to the Re-H bond homolysis and to the axial CO loss, respectively. The theoretical absorption spectrum is characterized by two bands, one intense peak centered at #lambda#=500 nm (21000 cm~(-1)) and one broad band centered at 310 nm (32 500 cm~(-1)). The visible band was assigned to the low-lying metal-to-ligand charge-transfer (MLCT) states with a main cotnribution fo the a~1A'->C~1A' trnsition corresponding to the 3d_(xz)->#pi#~*_(dab) excitation. The second band calculated in the UV energy domain was assigned to the d~1A' (#sigma#_(Mn-H)->#pi#~*_(dab)) state corresponding to a sigmabond-to-ligand charge-transfer (SBLCT) state. the photodisociation dynamics of the low-lying ~1MLCT and ~3SBLCT states following irradiation in the visible energy domain was simulated by wavepacket propagation on the two-dimensional diabatic potentials V(q_a, q_b) coupled by the spin-orbit. In contrast to what was found for the manganese analgue, the ~1MLCT state is nonreactive and a rather slow (beyond the pstime scale), nontotal and indirect homolysis fo the Re-H bond occurs through ~1MLCT->~3BSLCT interystem crossing.
机译：通过CASSCF / MR-CCI电势的波包传播研究了[Re（H）（CO）_3（H-dab）]（H-dab = 1,4-diaza-1,3-丁二烯）的光解动力学根据两个坐标q_a和Q_b的函数计算电子基态和低位激发态，这两个坐标分别对应于Re-H键均质化和轴向CO损失。理论吸收光谱的特征在于两个谱带，一个强峰集中在＃λ= 500 nm（21000 cm〜（-1）），一个宽谱带集中在310 nm（32 500 cm〜（-1））。可见带被分配到低层金属到配体的电荷转移（MLCT）状态，其主从动端对应于3d_（xz）->＃pi的a〜1A'-> C〜1A'传统＃〜* _（dab）激励。在UV能量域中计算出的第二条带被分配给d〜1A'（#sigma #_（Mn-H）->＃pi＃〜* _（dab））状态，该状态对应于sigmabond-to-ligand电荷-传输（SBLCT）状态。通过在自旋轨道耦合的二维绝热势V（q_a，q_b）上的波包传播，模拟了可见光域中低能级〜1MLCT和〜3SBLCT状态的光解离动力学。与发现的锰类似物相反，〜1MLCT状态是非反应性的，并且Re-H键通过〜1MLCT->〜3BSLCT系统间交叉而发生相当缓慢（超过pstime范围），非完全和间接均质化。

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