The time-dependent quantum dynamics calculation for reaction O(3P)+CH4 →CH3+OH is made, using of the semirigid vibrating rotor target (SVRT) model and the time-dependent wave packet (TDWP) method. The corresponding r...The time-dependent quantum dynamics calculation for reaction O(3P)+CH4 →CH3+OH is made, using of the semirigid vibrating rotor target (SVRT) model and the time-dependent wave packet (TDWP) method. The corresponding reaction probabilities of different initial states are provided. From the calculation of initial rovibrational statej=0,v=0, 1, we can see that the excitation of the H-CH3 stretching vibration gives significant enhancement of reaction probability and the reaction threshold decreases dramatically with the enhancement of the vibrating excitation, which indicates that the vibrating energy of reagent molecules contributes a lot to the molecular collision. As for the calculation of reaction probability of statev=0,j=0,1,2,3, the results show that the reaction probability rises significantly with the enhancement of rotational quantum numberj while the reaction threshold has no changes. The spatial steric effect of the title reaction is studied and analyzed too after the calculation of reaction probability of statesj=5,k=0–2,n=0 andj=5,k=2,n=0–2 is made.展开更多
The four-dimensional time-dependent quantum dynamics calculations for reactions of group IV hydride with H are carried out by employing the semirigid vibrating rotor target model and the time-dependent wave packet met...The four-dimensional time-dependent quantum dynamics calculations for reactions of group IV hydride with H are carried out by employing the semirigid vibrating rotor target model and the time-dependent wave packet method. The reaction possibility, cross section and rate constants for reactions (H+SiH_4 and H+GeH_4) in different initial vibrational and rotational states are obtained. The common feature for such kind of reaction process is summarized. The theoretical result is consistent with available measurement, which indicates the credibility of this theory and the potential energy surface.展开更多
Wave packet dynamics of the Li2 molecule are investigated by using the time-dependent quantum wave packet method, and the time-resolved photoelectron spectra of the Li2 molecule are calculated. The time-resolved wave ...Wave packet dynamics of the Li2 molecule are investigated by using the time-dependent quantum wave packet method, and the time-resolved photoelectron spectra of the Li2 molecule are calculated. The time-resolved wave packet theory is used to reasonably interpret the phenomena of the photoelectron spectra for different parameters. Our calculation shows that the loss of the wave packets in the shelf state area of E1∑g＋ plays a prominent role in the process of photoionization with the increase of the delay time. Moreover, the oscillation of the wave packet on the E1∑g＋ curve symbolizes a decreasing process of energy.展开更多
We present a state-to-state dynamical calculation on the reaction S++ H2→ SH+ +H based on an accurate X2 A″ potential surface. Some reaction properties, such as reaction probability, integral cross sections, product...We present a state-to-state dynamical calculation on the reaction S++ H2→ SH+ +H based on an accurate X2 A″ potential surface. Some reaction properties, such as reaction probability, integral cross sections, product distribution, etc.,are found to be those with characteristics of an indirect reaction. The oscillating structures appearing in reaction probability versus collision energy are considered to be the consequence of the deep potential well in the reaction. The comparison of the present total integral cross sections with the previous quasi-classical trajectory results shows that the quantum effect is more important at low collision energies. In addition, the quantum number inversion in the rotational distribution of the product is regarded as the result of the heavy–light–light mass combination, which is not effective for the vibrational excitation. For the collision energies considered, the product differential cross sections of the title reaction are mainly concentrated in the forward and backward regions, which suggests that there is a long-life intermediate complex in the reaction process.展开更多
State-to-state time-dependent quantum dynamics calculations are carried out to study F（2P） ＋ HO（2ЦП（→ O（3P） ＋ HF（1∑＋） reaction on 1^3A″ ground potential energy surface （PES）. The vibrationally resolv...State-to-state time-dependent quantum dynamics calculations are carried out to study F（2P） ＋ HO（2ЦП（→ O（3P） ＋ HF（1∑＋） reaction on 1^3A″ ground potential energy surface （PES）. The vibrationally resolved reaction probabilities and the total integral cross section agree well with the previous results. Due to the heavy-light-heavy （HLH） system and the large exoergicity, the obvious vibrational inversion is found in a state-resolved integral cross section. The total differential cross section is found to be forward-backward scattering biased with strong oscillations at energy lower than a threshold of 0.10 eV, which is the indication of the indirect complex-forming mechanism. When the collision energy increases to greater than 0.10 eV, the angular distribution of the product becomes a strong forward scattering, and almost all the products are distributed at θt = 0°. This forward-peaked distribution can be attributed to the larger J partial waves and the property of the F atom itself, which make this reaction a direct abstraction process. The state-resolved differential cross sections are basically forward-backward symmetric for v′ = 0, 1, and 2 at a collision energy of 0.07 eV; for a collision energy of 0.30 eV, it changes from backward/sideward scattering to forward peaked as v′ increasing from 0 to 3. These results indicate that the contribution of differential cross sections with more highly vibrational excited states to the total differential cross sections is principal, which further verifies the vibrational inversion in the products.展开更多
The quantum state-to-state calculations of the D + ND→N + D_2 reaction are performed on a potential energy surface of 4 A'' state. The state-resolved integral and differential cross sections and product state...The quantum state-to-state calculations of the D + ND→N + D_2 reaction are performed on a potential energy surface of 4 A'' state. The state-resolved integral and differential cross sections and product state distributions are calculated and discussed. It is found that the rotational distribution, rather than the vibrational distribution, of the product has an obvious inversion. Due to the fact that it is a small-impact-parameter collision, its product D_2 is mainly dominated by rebound mechanism, which can lead to backward scattering at low collision energy. As the collision energy increases, the forward scattering and sideward scattering begin to appear. In addition, the backward collision is also found to happen at high collision energy, through which we can know that both the rebound mechanism and stripping mechanism exist at high collision energy.展开更多
Dynamics of the Au + H2 reaction are studied using time-dependent wave packet(TDWP) and quasi-classical trajectory(QCT) methods based on a new potential energy surface [Int. J. Quantum Chem. 118 e25493(2018)]. The dyn...Dynamics of the Au + H2 reaction are studied using time-dependent wave packet(TDWP) and quasi-classical trajectory(QCT) methods based on a new potential energy surface [Int. J. Quantum Chem. 118 e25493(2018)]. The dynamic properties such as reaction probability, integral cross section, differential cross section and the distribution of product are studied at state-to-state level of theory. Furthermore, the present results are compared with the theoretical studies available.The results indicate that the complex-forming reaction mechanism is dominated in the reaction in the low collision energy region and the abstract reaction mechanism plays a dominant role at high collision energies. Different from previous theoretical calculations, the side-ways scattering signals are found in the present work and become more and more apparent with increasing collision energy.展开更多
The N（2D） ＋ HD （v = 0, j = 0） reaction has been studied by a quantum time-dependent wave packet approach with a second-order split operator on the potential energy surface of Li et al. （Li Y, Yuan J, Chen M, Ma ...The N（2D） ＋ HD （v = 0, j = 0） reaction has been studied by a quantum time-dependent wave packet approach with a second-order split operator on the potential energy surface of Li et al. （Li Y, Yuan J, Chen M, Ma F and Sun M J. Comput. Chem. 34 1686）. The rovibrationally resolved reaction probability, vibrationally integral cross section, and differential cross section of the NH ＋ D and ND ＋ H channel are investigated at the state-to-state level of theory. The experimental data of the thermal rate constant of two output channels is very scare, but the sum of the two output channels is in excellent agreement with the experimental data which was reported by Umemoto et al. It may imply that the thermal rate constants of the two output channels are accurate and reliable.展开更多
Quantum state-to-state dynamics of the N(4S) + H-2(X1+Σ) → NH(X3Σ) + H(2S) reaction is reported in an accurate novel potential energy surface constructed by Zhai et al.(2011 J. Chem. Phys. 135 104314). The time-dep...Quantum state-to-state dynamics of the N(4S) + H-2(X1+Σ) → NH(X3Σ) + H(2S) reaction is reported in an accurate novel potential energy surface constructed by Zhai et al.(2011 J. Chem. Phys. 135 104314). The time-dependent wave packet method, which is implemented on graphics processing units, is used to calculate the differential cross sections. The influences of the collision energy on the product state-resolved integral cross sections and total differential cross sections are calculated and discussed. It is found that the products NH are predominated by the backward scattering due to the small impact parameter collisions, with only minor components being forward and sideways scattered, and have an inverted rotational distribution and no inversion in vibrational distributions; both rebound and stripping mechanisms exist in the case of high collision energies.展开更多
基金This work was supported by the National Natural Science Foundation of China(No.22273104,No.22022306,No.22288201)the Innovation Program for Quantum Science and Technology(No.2021ZD 0303305)+2 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB0450202)Liaoning Revitalization Talents Program(No.XLYC 2203062)the Dalian Innovation Support Program(No.2021RD05).
基金supported by the National Natural Science Foundation of China(Grant Nos.19874040 and 10174046).
文摘The time-dependent quantum dynamics calculation for reaction O(3P)+CH4 →CH3+OH is made, using of the semirigid vibrating rotor target (SVRT) model and the time-dependent wave packet (TDWP) method. The corresponding reaction probabilities of different initial states are provided. From the calculation of initial rovibrational statej=0,v=0, 1, we can see that the excitation of the H-CH3 stretching vibration gives significant enhancement of reaction probability and the reaction threshold decreases dramatically with the enhancement of the vibrating excitation, which indicates that the vibrating energy of reagent molecules contributes a lot to the molecular collision. As for the calculation of reaction probability of statev=0,j=0,1,2,3, the results show that the reaction probability rises significantly with the enhancement of rotational quantum numberj while the reaction threshold has no changes. The spatial steric effect of the title reaction is studied and analyzed too after the calculation of reaction probability of statesj=5,k=0–2,n=0 andj=5,k=2,n=0–2 is made.
基金This work was supported in part by the National Natural Science Foundation of China (Grant Nos. 10174046, 10474060 and 10504017).
文摘The four-dimensional time-dependent quantum dynamics calculations for reactions of group IV hydride with H are carried out by employing the semirigid vibrating rotor target model and the time-dependent wave packet method. The reaction possibility, cross section and rate constants for reactions (H+SiH_4 and H+GeH_4) in different initial vibrational and rotational states are obtained. The common feature for such kind of reaction process is summarized. The theoretical result is consistent with available measurement, which indicates the credibility of this theory and the potential energy surface.
基金Project supported by the National Natural Science Foundation of China (Grant Nos. 60977063 and 10574039)the Foundation for Key Program of Ministry of Education China (Grant No. 206084)+1 种基金the Innovation Scientists and Technicians Troop Construction Projects of Henan Province,China (Grant No. 084100510011)the Innovation Talents of Institution of Higher Education of Henan Province,China (Grant No. 2006KYCX002)
文摘Wave packet dynamics of the Li2 molecule are investigated by using the time-dependent quantum wave packet method, and the time-resolved photoelectron spectra of the Li2 molecule are calculated. The time-resolved wave packet theory is used to reasonably interpret the phenomena of the photoelectron spectra for different parameters. Our calculation shows that the loss of the wave packets in the shelf state area of E1∑g＋ plays a prominent role in the process of photoionization with the increase of the delay time. Moreover, the oscillation of the wave packet on the E1∑g＋ curve symbolizes a decreasing process of energy.
基金National Natural Science Foundation of China(Grant No.11674198)the Taishan Scholar Project of Shandong Province,China(Grant No.ts201511025)the Science Fund from the Shandong Provincial Laboratory of Biophysics.
文摘We present a state-to-state dynamical calculation on the reaction S++ H2→ SH+ +H based on an accurate X2 A″ potential surface. Some reaction properties, such as reaction probability, integral cross sections, product distribution, etc.,are found to be those with characteristics of an indirect reaction. The oscillating structures appearing in reaction probability versus collision energy are considered to be the consequence of the deep potential well in the reaction. The comparison of the present total integral cross sections with the previous quasi-classical trajectory results shows that the quantum effect is more important at low collision energies. In addition, the quantum number inversion in the rotational distribution of the product is regarded as the result of the heavy–light–light mass combination, which is not effective for the vibrational excitation. For the collision energies considered, the product differential cross sections of the title reaction are mainly concentrated in the forward and backward regions, which suggests that there is a long-life intermediate complex in the reaction process.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11504206 and 11404049)the China Postdoctoral Science Foundation(CPSF)(Grant No.2014M561259)the Ph.D.Research Start-up Fund of Shandong Jiaotong University
文摘State-to-state time-dependent quantum dynamics calculations are carried out to study F（2P） ＋ HO（2ЦП（→ O（3P） ＋ HF（1∑＋） reaction on 1^3A″ ground potential energy surface （PES）. The vibrationally resolved reaction probabilities and the total integral cross section agree well with the previous results. Due to the heavy-light-heavy （HLH） system and the large exoergicity, the obvious vibrational inversion is found in a state-resolved integral cross section. The total differential cross section is found to be forward-backward scattering biased with strong oscillations at energy lower than a threshold of 0.10 eV, which is the indication of the indirect complex-forming mechanism. When the collision energy increases to greater than 0.10 eV, the angular distribution of the product becomes a strong forward scattering, and almost all the products are distributed at θt = 0°. This forward-peaked distribution can be attributed to the larger J partial waves and the property of the F atom itself, which make this reaction a direct abstraction process. The state-resolved differential cross sections are basically forward-backward symmetric for v′ = 0, 1, and 2 at a collision energy of 0.07 eV; for a collision energy of 0.30 eV, it changes from backward/sideward scattering to forward peaked as v′ increasing from 0 to 3. These results indicate that the contribution of differential cross sections with more highly vibrational excited states to the total differential cross sections is principal, which further verifies the vibrational inversion in the products.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11674198 and 11504206)the Natural Science Foundation of Shandong Province,China(Grant No.ZR2016AP14)the Taishan Scholar Project of Shandong Province,China
文摘The quantum state-to-state calculations of the D + ND→N + D_2 reaction are performed on a potential energy surface of 4 A'' state. The state-resolved integral and differential cross sections and product state distributions are calculated and discussed. It is found that the rotational distribution, rather than the vibrational distribution, of the product has an obvious inversion. Due to the fact that it is a small-impact-parameter collision, its product D_2 is mainly dominated by rebound mechanism, which can lead to backward scattering at low collision energy. As the collision energy increases, the forward scattering and sideward scattering begin to appear. In addition, the backward collision is also found to happen at high collision energy, through which we can know that both the rebound mechanism and stripping mechanism exist at high collision energy.
文摘Dynamics of the Au + H2 reaction are studied using time-dependent wave packet(TDWP) and quasi-classical trajectory(QCT) methods based on a new potential energy surface [Int. J. Quantum Chem. 118 e25493(2018)]. The dynamic properties such as reaction probability, integral cross section, differential cross section and the distribution of product are studied at state-to-state level of theory. Furthermore, the present results are compared with the theoretical studies available.The results indicate that the complex-forming reaction mechanism is dominated in the reaction in the low collision energy region and the abstract reaction mechanism plays a dominant role at high collision energies. Different from previous theoretical calculations, the side-ways scattering signals are found in the present work and become more and more apparent with increasing collision energy.
文摘The N（2D） ＋ HD （v = 0, j = 0） reaction has been studied by a quantum time-dependent wave packet approach with a second-order split operator on the potential energy surface of Li et al. （Li Y, Yuan J, Chen M, Ma F and Sun M J. Comput. Chem. 34 1686）. The rovibrationally resolved reaction probability, vibrationally integral cross section, and differential cross section of the NH ＋ D and ND ＋ H channel are investigated at the state-to-state level of theory. The experimental data of the thermal rate constant of two output channels is very scare, but the sum of the two output channels is in excellent agreement with the experimental data which was reported by Umemoto et al. It may imply that the thermal rate constants of the two output channels are accurate and reliable.
基金supported by the National Natural Science Foundation of China(Grant No.11074151)the Natural Science Foundation of Shandong Province,China(Grant No.ZR2014AM022)
文摘Quantum state-to-state dynamics of the N(4S) + H-2(X1+Σ) → NH(X3Σ) + H(2S) reaction is reported in an accurate novel potential energy surface constructed by Zhai et al.(2011 J. Chem. Phys. 135 104314). The time-dependent wave packet method, which is implemented on graphics processing units, is used to calculate the differential cross sections. The influences of the collision energy on the product state-resolved integral cross sections and total differential cross sections are calculated and discussed. It is found that the products NH are predominated by the backward scattering due to the small impact parameter collisions, with only minor components being forward and sideways scattered, and have an inverted rotational distribution and no inversion in vibrational distributions; both rebound and stripping mechanisms exist in the case of high collision energies.
