发表机构
NeuroTechNet S.A.S.; Quantum and Computational Chemistry Group (QCCG), Universidad Nacional de Colombia（NeuroTechNet S.A.S.; 哥伦比亚国立大学量子与计算化学组）
机构由 AI 辅助整理，请以论文原文为准。AI 中文总结
该工作将DMRG-QD-NEVPT2解析梯度与非绝热耦合部署于消费级GPU，实现穿越圆锥交叉的多态动力学模拟，恢复动态相关并给出正确的NACME。
AI 中文摘要
通过圆锥交叉的非绝热动力学需要静态和动态相关性，并且在每个几何构型下需要激发态梯度和态间非绝热耦合（NACME）；在此水平上的解析多参考导数此前仅能在集群规模上实现。我们报道了基于B2PLYP双杂化Kohn-Sham轨道的器件驻留DMRG-QD-NEVPT2及其解析导数：密度矩阵重整化群参考提供静态相关性，而准简并NEVPT2通过多态有效哈密顿量补充动态相关性，该哈密顿量在交叉点处仍然有效，而单态微扰理论在此失效。每个梯度和NACME都是收缩图的逆向模式转置，该收缩图将DMRG扫描作为无规范、无磁带的节点，并简化为带有Cholesky因子的活性空间RDM收缩。整个构建在消费级8GB GPU上运行。DMRG参考在活性空间内达到FCI精度至$10^{-15}$，单精度部分在光谱学上惰性（$<10^{-6}$ eV）；该修正产生平滑的绝热势能面和非零的、呈$1/\Delta E$发散的NACME，穿越扭曲乙烯交叉点——而绝热线性响应TDDFT在此返回零——并恢复了离子性$\pi\pi^*$态所需的动态相关性。DMRG-NEVPT2和准简并NEVPT2各自已确立；本贡献在于整个技术栈——穿越圆锥交叉的多态方法，具有解析梯度和耦合——在商品硬件上实现器件驻留。这是我们同一引擎的密度泛函实现的伴随多参考版本。
英文摘要
Nonadiabatic dynamics through a conical intersection requires both static and dynamic correlation and, at every geometry, an excited-state gradient and interstate nonadiabatic coupling (NACME). Analytic multireference derivatives at this level have been confined to datacenter-scale hardware. We report device-resident \mbox{DMRG-QD-NEVPT2} with analytic gradients and NACMEs within the $8$\,GB of a consumer GPU: a density-matrix-renormalization-group (DMRG) active-space reference supplies the static correlation, and quasi-degenerate SC-NEVPT2 dresses it through a multi-state effective Hamiltonian that remains valid \emph{through} a conical intersection, where single-state perturbation theory develops a vanishing denominator and fails. Every gradient and NACME is one reverse-mode transpose of a single contraction graph: the DMRG sweep enters as a gauge-free differentiable node, and all two-electron work is AO-direct through Cholesky factors. The DMRG reference is exact within the active space ($\sim\!10^{-15}$\,Ha). The corrected adiabats close smoothly to a real $S_0/S_1$ conical intersection with a non-vanishing, $1/ΔE$-divergent NACME---where linear-response TDDFT returns zero identically---and the dressing restores the differential dynamic correlation that ionic $ππ^*$ states require. DMRG-NEVPT2 and quasi-degenerate NEVPT2 are each established; what is new is the combined stack---multi-state and through a conical intersection, with analytic gradients and couplings---realized device-resident on commodity hardware.
Comments22 pages, 11 figures
