Potentials of mean force fail to describe chemical bond-breaking in solution

Many liquid phase studies assume that the potential energy surfaces of reacting molecules are the same as in the gas phase, neglecting complex solvent dynamics that can completely alter the nature of chemical reactivity. Even studies that include solvent effects typically only consider them in an average, equilibrium way as part of a potential of mean force (PMF). In this work, we use mixed quantum/classical simulations to compare how equilibrium and non-equilibrium solvent motions affect the photodissociation of a simple diatomic molecule, NaK+, in liquid tetrahydrofuran. A PMF analysis shows that as the excited-state molecule dissociates with the solvent at equilibrium, the bonding electron remains associated with K+ at short bond distances but eventually localizes on Na+ at the end of dissociation.  When we examine nonequilibrium dynamical photodissociation trajectories, however, we find that they fall into three distinct categories: about a quarter of them have the bonding elec..., , # Data from: Potentials of mean force fail to describe chemical bond-breaking in solution

Dataset DOI: [10.5061/dryad.vhhmgqp63](10.5061/dryad.vhhmgqp63)

## Description of the data and file structure

### Files and variables

#### File: repository_upload.zip

**Description:** 

This zip file contains this READ.ME and 3 folders, described below

1. eqb_PMF (folder)

* Contains the equilibrium umbrella sampling trajectories with bond distance held at 4.00 to 7.75 angstroms, increment by 0.25 angstroms
* Sub-folder name is the corresponding bond distance in angstroms (e.g., the sub-folder named 4.00 contains data for Na--K bond held at 4.00 angstroms)
* Each distance sub-folder contains:
* The xyz files (e.g., dist4.00.xyz is the xyz file for Na--K bond distance held at 4.00 angstroms, located in sub-folder 4.00)
* First electronic excited state wavefunction cube file (es_wavefunction.cube)
* 1st shell THF coordination number (THF_CN.txt): the first column is time (in fs), the seco...,

诸多液相研究均默认反应分子的势能面与气相一致，却忽略了能够彻底改变化学反应本质的复杂溶剂动力学效应。即便考虑了溶剂效应的研究，通常也仅将其作为平均平衡态的因素纳入平均力势（Potential of Mean Force, PMF）中进行处理。本研究采用混合量子/经典模拟方法，对比平衡态与非平衡态溶剂运动对液态四氢呋喃（Tetrahydrofuran, THF）中简单双原子分子NaK+光解离过程的影响。平均力势分析结果表明，当溶剂处于平衡态时，激发态分子随溶剂解离，成键电子在键长较短时仍与K+结合，但在解离结束时最终定域于Na+。然而在分析非平衡态动力学光解离轨迹时，我们发现这些轨迹可分为三类：约四分之一的轨迹中成键电子……，# 数据来源：平均力势无法描述溶液中的化学键断裂过程
数据集DOI：[10.5061/dryad.vhhmgqp63](10.5061/dryad.vhhmgqp63)

## 数据与文件结构说明
### 文件与变量
#### 文件：repository_upload.zip
**文件说明：**
该压缩包包含本README文件与如下三个文件夹：
1. eqb_PMF（文件夹）
* 包含平衡态伞形采样轨迹，键长固定于4.00至7.75埃，步长为0.25埃
* 子文件夹以对应的键长（单位：埃）命名（例如，名为4.00的子文件夹包含Na-K键长固定为4.00埃的相关数据）
* 每个键长子文件夹包含以下内容：
* XYZ格式文件（例如，位于4.00子文件夹中的dist4.00.xyz即为Na-K键长固定为4.00埃的XYZ文件）
* 第一电子激发态波函数cube文件（es_wavefunction.cube）
* 第一溶剂化层四氢呋喃（THF）配位数文件（THF_CN.txt）：第一列为时间（单位：飞秒fs），第二列……