We compute highly accurate first principle based \textit{ab initio} adiabatic potential energy surfaces (PESs) using State-Averaged Multi-Configurational Self-Consistent Field (SA-MCSCF) followed by internally contracted Multi-Reference Configuration Interaction method incorporating fixed-reference Davidson corrections [ic-MRCI(Q)], where a full valence active space of 18 electrons in 12 orbitals and aug-cc-pVQZ basis set are employed for the low-lying four singlet electronic states of ozone ($\tilde{X}^1A'$, $1~^1A''$, $1~^1A'$ and $2^1A''$). It accurately reproduces the dissociation energies of ozone (1.101 eV) as well as the molecular oxygen (5.106 eV) along with vibrational frequencies of O$_3$ in comparison with experimental data. To ensure appropriate accuracy and proper convergence in the interaction as well as asymptotic regions, we (a) extend the number of electronic states in SA-MCSCF calculation (singlet as well as triplet and quintet); (b) systematically expand the active space [(12e,9o) $\rightarrow$ (18e,12o) $\rightarrow$ (24e,15o)] and basis set size (AVDZ $\rightarrow$ AV6Z $\rightarrow$ Complete Basis Set limit); (c) incorporate multi-reference character along with Davidson correction. Conical intersections between the adjacent electronic states (1-2, 2-3 and 3-4) are located at \textit{C}$_{2v}$, \textit{D}$_{3h}$ as well as \textit{C}$_{s}$ geometries through the four-state adiabatic-to-diabatic transformation of non-adiabatic coupling terms (NACTs) computed at Coupled-Perturbed Multi-Configurational Self-Consistent Field (CP-MCSCF) method along the circular contours. Finally, we present: (a) ic-MRCI(Q) calculated minimum energy path of incoming oxygen to the diatom (O$_2$) is devoid of any ``reef'' feature; (b) NACTs and diabatic PES matrix elements as function of hyperangles ($θ$,$ϕ$) at a fixed hyperradius $ρ= 4$ Bohr for a four state sub-Hilbert space.
Construction of First Principle Based Adiabatic and Diabatic Hamiltonian for TiO$_6^{8-}$ unit of BaTiO$_3$ Crystal: Photoemission Spectra and Ferroelectricity
A Robust and Unified Solution for Choosing the Phases of Adiabatic States as a Function of Geometry: Extending Parallel Transport Concepts to the cases of Trivial & Near Trivial Crossings
Effect of the avoided crossing on the rovibrational energy levels, resonances, and predissociation lifetimes within the ground and first excited electronic states of lithium fluoride
M. V. Lomonosov Moscow State University（莫斯科国立罗蒙诺索夫大学）
Reduced density matrix functional theory from an ab initio seniority-zero wave function: Exact and approximate formulations along adiabatic connection paths
Spin-orbit transitions in the N$^+$($^3P_{J_A}$) + H$_2$ $\rightarrow$ NH$^+$($X^2Π$, $^4Σ^-$)+ H($^2S$) reaction, using adiabatic and mixed quantum-adiabatic statistical approaches
用两种统计方法计算了N-$^+$（$^3P_{J_A}$）所有自旋轨道态的反应截面和速率常数，一种是纯绝热方法，另一种是对入射通道进行混合量子俘获，对产物通道进行绝热处理.这是通过使用一个对称性调整的基础设置结合电子（自旋和轨道）和核角动量的反应物通道。为此，精确的{ \it从头计算}计算分别进行反应物和产品。在反应物通道中，三个最低的电子状态（没有自旋-轨道耦合）已被非线性化，并已通过一个模型引入自旋-轨道耦合，该模型将自旋-轨道相互作用定位在N $^+$原子中，与包括自旋-轨道耦合的{ \it ab initio}计算相比，该模型产生了准确的结果。用\it从头计算方法确定了产物的11个纯绝热自旋轨道态。由此获得的反应速率常数是非常好的协议与现有的实验数据为几个邻-H $_2$馏分，假设热初始分布的自旋轨道状态。获得了选定的自旋-轨道$J_A$态的速率常数，以提供适当的自旋-轨道效应的验证，从而获得实验速率常数。
Photodissociation dynamics in the first absorption band of pyrrole: II. Photofragment distributions for the $^1\!A_2(πσ^*) \leftarrow \tilde{X}^1\!A_1(ππ)$ transition
Theoretical description of adiabatic laser alignment and mixed-field orientation: the need for a non-adiabatic model
本文对非对称陀螺分子的激光取向和混合场取向实验进行了理论研究。在这些实验中，摆动态是利用来自脉冲激光器的线性极化强交流电场与弱静电场相结合而产生的。我们比较了我们的计算结果与实验结果获得的原型大分子苯甲腈（C $_7$ H $_5$ N）[J. L. Hansen等人，Phys.Rev.A，83，023406（2011）]，并探索了几种场配置的分子系综的方向性质，即，适用于交流场和直流场之间的各种场强和角度。对于垂直场，得到纯对准，这是很好地再现了模拟。对于倾斜场，我们表明，一个完全绝热的描述的过程中没有重现实验观察到的方向，它是强制性的使用非绝热模型的旋转状态之间的人口转移。我们开发了这样一个模型，并将其结果与实验数据进行比较，证实了非绝热过程在场修饰分子动力学中的重要性。
