论文标题
新的CCSD(T)机器学习PES上的量子计算揭示了气相$ trans $和$ gauche $ ethanol conformers的泄漏性质
Quantum calculations on a new CCSD(T) machine-learned PES reveal the leaky nature of gas-phase $trans$ and $gauche$ ethanol conformers
论文作者
论文摘要
乙醇是燃烧,天体化学和凝结相的基本兴趣分子。它的特征是两个甲基转子和$ trans $($ anti $)和$ gauche $构型,它们的能量非常接近。在这里,我们表明,基于对振动零点状态的严格量子计算,使用新的启动势能表面(PES),基态类似于$ trans $ conformer,但存在于$ gauche $ conformer的实质性)。这解释了有关两个构象体的识别和隔离的实验问题。当剥离OH组时,这种“泄漏”效果会部分淬灭,这进一步证明了需要进行量子机械方法。扩散蒙特卡洛(DMC)和全维半经典动力学计算。新的PES是通过$δ$ - 机器学习方法从先前存在的低水平(LL)密度功能理论(DFT)表面获得的。该表面使用相对少量的$ ab $ $ $ $ $ $ ccsd(t)能量将CCSD(T)理论水平带入理论水平。校正后的PES与Direct $ ab $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $ $的协议非常好。还报道了针对$ trans $ - $ gauche $扭转运动的一维离散变量表示计算,这与实验合理地达成了一致。
Ethanol is a molecule of fundamental interest in combustion, astrochemistry, and condensed phase as a solvent. It is characterized by two methyl rotors and $trans$ ($anti$) and $gauche$ conformers, which are known to be very close in energy. Here we show that based on rigorous quantum calculations of the vibrational zero-point state, using a new ab initio potential energy surface (PES), the ground state resembles the $trans$ conformer but substantial delocalization to the $gauche$ conformer is present. This explains experimental issues about the identification and isolation of the two conformers. This "leak" effect is partially quenched when deuterating the OH group, which further demonstrates the need for a quantum mechanical approach. Diffusion Monte Carlo (DMC) and full-dimensional semiclassical dynamics calculations are employed. The new PES is obtained by means of a $Δ$-Machine learning approach starting from a pre-existing low level (LL) density functional theory (DFT) surface. This surface is brought to the CCSD(T) level of theory using a relatively small number of $ab$ $initio$ CCSD(T) energies. Agreement between the corrected PES and direct $ab$ $initio$ results for standard fidelity tests is excellent. One- and two-dimensional discrete variable representation calculations focusing on the $trans$-$gauche$ torsional motion are also reported, in reasonable agreement with the experiment.