本文選題：探針分子 + 線性/二維紅外光譜��； 參考：《吉林大學(xué)》2017年碩士論文

【摘要】：將分子的某個(gè)特殊位點(diǎn)作為探針來研究其振子所處環(huán)境的一維和二維紅外光譜對在分子層面上理解在凝聚相以及生物體系中的局域氫鍵網(wǎng)絡(luò),組態(tài)動(dòng)力學(xué)以及長程靜電相互作用都有特殊意義。然而,到目前為止,由于超快的時(shí)間尺度、核的量子效應(yīng)以及大尺度分子處于復(fù)雜的環(huán)境中等原因,導(dǎo)致對于實(shí)驗(yàn)光譜的量子解釋仍然是一個(gè)巨大的挑戰(zhàn)。為實(shí)現(xiàn)這個(gè)目標(biāo),其中一個(gè)重要的困難是計(jì)算時(shí)間依賴的振動(dòng)躍遷頻率,并且這個(gè)頻率的計(jì)算得包含振動(dòng)運(yùn)動(dòng)的量子效應(yīng)。在我的這個(gè)工作中,我們提出了一種快速并且精確的新方法來重現(xiàn)一維和二維的紅外光譜——量子振動(dòng)微擾(Quantum Vibrational Perturbation,QVP)。該方法主要是為了提升計(jì)算分子中生色基團(tuán)的瞬時(shí)量子振動(dòng)頻率的精度和效率。該方法是將經(jīng)典取樣和利用量子力學(xué)獲得某一特殊振動(dòng)模的躍遷頻率相結(jié)合的一種半經(jīng)典的方法。經(jīng)典取樣主要是利用經(jīng)典的從頭算分子動(dòng)力學(xué)來獲得分子間的構(gòu)型密度分布,而這里的量子效應(yīng)主要是通過一階微擾近似來將量子效應(yīng)包含在振動(dòng)躍遷頻率的計(jì)算中。用離散變分格點(diǎn)的方法來描述振動(dòng)基態(tài)與激發(fā)態(tài)的波函數(shù),使得計(jì)算的效率大大地提高,而微擾方法是用來獲得由于溶劑環(huán)境漲落而導(dǎo)致的振動(dòng)頻率位移,同時(shí)其也避免了解薛定諤方程,提高了振動(dòng)頻率獲得的效率。量子力學(xué)/分子力學(xué)聯(lián)合勢能將用于對溶液環(huán)境的模擬,其也將大大降低了分子動(dòng)力學(xué)勢能的計(jì)算,進(jìn)而使得該方法在大生物蛋白分子中的應(yīng)用成為可能。我們發(fā)現(xiàn)一階微擾,對于該計(jì)算已經(jīng)足夠精確了,進(jìn)而獲得基于從頭算分子動(dòng)力學(xué)軌跡的振動(dòng)頻率。本文同時(shí)也提出了量子振動(dòng)微擾方法在氯化氫-水團(tuán)簇以及在丙酮水溶液中的應(yīng)用,并且分別得到了在氯化氫-水團(tuán)簇體系中的氯氫伸縮振動(dòng)的一維和二維紅外光譜以及丙酮水溶液中的羰基伸縮振動(dòng)的一維紅外光譜。為了進(jìn)一步降低計(jì)算成本,我們提出了一種雜化的策略,并且我們發(fā)現(xiàn)通過該策略計(jì)算得到的峰的位置和形狀都與實(shí)驗(yàn)結(jié)果符合地非常好。另外,我們發(fā)現(xiàn)了在氯氫伸縮振動(dòng)模中,非諧效應(yīng)起到了重要的作用,而氫鍵相互作用加劇了這種非諧效應(yīng)。
[Abstract]:A special site of the molecule is used as a probe to study the local hydrogen bond network in the condensed phase and in the biological system at the molecular level. Configuration dynamics and long-range electrostatic interaction are of special significance. However, the quantum interpretation of experimental spectra is still a great challenge due to the ultrafast time scale, the quantum effects of nuclei and the large scale molecules in complex environments. In order to achieve this goal, one of the important difficulties is to calculate the time-dependent vibration transition frequency, and the calculation of this frequency includes the quantum effect of vibration motion. In my work, we propose a fast and accurate new method to reproduce the quantum Vibrational perturbation QVPs of one and two dimensional infrared spectra, Quantum Vibrational Perturation, Quantum Vibrational Perturation, Quantum Vibrational Perturation, Quantum Vibrational Perturation, Quantum Vibrational Perturation, and Quantum Vibrational Perturation. The main purpose of this method is to improve the accuracy and efficiency of calculating the instantaneous quantum vibration frequency of chromophore groups in molecules. This method is a semiclassical method which combines classical sampling with obtaining the transition frequency of a special vibration mode by quantum mechanics. Classical sampling mainly uses the classical ab initio molecular dynamics to obtain the density distribution of the intermolecular configuration, and the quantum effect is mainly included in the calculation of the vibrational transition frequency by the first-order perturbation approximation. The method of discrete variational lattice points is used to describe the wave functions of the ground and excited states of vibration. The efficiency of calculation is greatly improved, while the perturbation method is used to obtain the vibration frequency displacement caused by the fluctuation of the solvent environment. At the same time, it avoids the understanding of Schrodinger equation and improves the efficiency of vibration frequency. The combined potential energy of quantum mechanics and molecular mechanics will be used to simulate the solution environment, which will greatly reduce the calculation of molecular dynamics potential energy. We find that the first order perturbation is accurate enough for this calculation, and then the vibration frequency based on ab initio molecular dynamics locus is obtained. At the same time, the application of quantum vibration perturbation method in hydrogen chloride water cluster and acetone aqueous solution is also presented. The one dimensional and two dimensional infrared spectra of the stretching vibration of hydrogen chloride and water cluster system and the one dimensional infrared spectrum of the stretching vibration of carbonyl group in acetone aqueous solution were obtained respectively. In order to further reduce the computational cost, we propose a hybrid strategy, and we find that the position and shape of the calculated peaks are in good agreement with the experimental results. In addition, we find that the anharmonic effect plays an important role in the chlorohydrogen stretching vibration mode, and the hydrogen bond interaction intensifies the anharmonic effect.
【學(xué)位授予單位】：吉林大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O645.1

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