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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Interlocking Tripelt Electronic States of Isocyanic Acid: Sources of Nonadiabatic Photofragmentation Dynamics
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Interlocking Tripelt Electronic States of Isocyanic Acid: Sources of Nonadiabatic Photofragmentation Dynamics

机译：异氰酸互锁的Tripelt电子态：非绝热光裂解动力学的来源

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The triplet electronic states of isocyanic acid have been systematically investigated by means ofstate-of- the-art electronic structure methods. including various correlation techniques based on the coupled-cluster ansatz {CCSD, EOM-CCSD, CCSD(T), and BD(TQ)]. second- through fifth-order M~ller-Plesset perturbation theory (MP2-MP5), and the complete active space self-consistent field approach. The one-particle [(C,N,O)/ H] basis sets for these studies ranged in quality from [4s2pld/2slp] k> [7s6p5d4f3g2hli/6s5p4d3f2glh]. Vertical excitation energies were determined for the lowest 13 triplet states (5 valence. 8 Rydberg), and potential energy curves for bending to and from linearity were generated for 10of these states, revealing intricate state interactions and numerous actual and avoided crossings. An extensive mapping was then executed for the interlocking a3A" and i)3A' surfaces, which produced geometric structures, relative energies. harmonic vibrational frequencies, and selected large-amplitude vibrational eigenstates. for torsional conformers. inversion barriers, fragmentation barriers, dissociation products, and ionization limits. in addition to identifying intermingled conical intersections. The lowest-energy conformer on the a3A" surface is actually a skewed (CI) structure with a torsion angle of 143°, a barrier to planarity of only 74 cm-1, an adiabatic excitation energy near To = 30056 cm-1, and an exit barrier for 3NH + CO fragmentation of only about Ll~ = 3252 cm-1.. It is discovered that there are actually no legitimate minima (removed from conical intersections) on the b3A' surface, because in-plane optimizations bring associated structures below the companion 3A" state and subsequently connect them to the lowest triplet surface via torsional excursions along imaginary-frequency normal modes.
机译：借助于最新的电子结构方法，系统地研究了异氰酸的三重态电子态。包括基于耦合簇ansatz {CCSD，EOM-CCSD，CCSD（T）和BD（TQ）]的各种相关技术。二阶到五阶M〜ller-Plesset微扰理论（MP2-MP5），以及完整的有源空间自洽场方法。这些研究的单粒子[（C，N，O）/ H]基集的质量范围从[4s2pld / 2slp] k> [7s6p5d4f3g2hli / 6s5p4d3f2glh]。确定了最低的13个三重态（5价8 Rydberg）的垂直激发能，并针对其中10个态生成了线性折弯的势能曲线，揭示了复杂的状态相互作用以及许多实际的和避免的交叉。然后对互锁的a3A“和i）3A'表面执行了广泛的映射，生成了几何结构，相对能量，谐波振动频率，并为扭转形变体选择了大振幅振动本征态。反转屏障，碎裂屏障，解离产物除了识别出圆锥形的交叉点外，a3A“表面上的最低能量构象体实际上是扭曲（CI）结构，其扭转角为143°，对平面的障碍仅为74 cm-1， To = 30056 cm-1附近的绝热激发能，3NH + CO碎片的出口壁垒仅为Ll〜= 3252 cm-1。发现，实际上在其上没有合法的极小值（从圆锥形相交处去除）。 b3A'表面，因为平面内优化将关联的结构置于伴随的3A“状态以下，并随后通过沿图像的扭转偏移将它们连接到最低的三重态表面单频普通模式。

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