This paper calculates the five most stable conformers of serine with Hartree-Fock theory, density functional theory （B3LYP）, Moller-Plesset perturbation theory （MP4（SDQ）） and electron propagation theory with the...This paper calculates the five most stable conformers of serine with Hartree-Fock theory, density functional theory （B3LYP）, Moller-Plesset perturbation theory （MP4（SDQ）） and electron propagation theory with the 6-311＋＋G（2d,2p） basis set. The calculated vertical ionization energies for the valence molecular orbitals of each conformer are in agreement with the experimental data, indicating that a range of molecular conformations would coexist in an equilibrium sample. Information of the five outer valence molecular orbitals for each conformer is explored in coordinate and momentum spaces using dual space analysis to investigate the conformational processes, which are generated from the global minimum conformer Serl by rotation of C2-C3 （Ser4）, C1 C2 （Ser5） and C1-O2 （Set2 and Ser3）. Orbitals 28a, 27a and 26a are identified as the fingerprint orbitals for all the conformational processes.展开更多
This paper studies the molecular rotational excitation and field-free spatial alignment in a nonresonant intense laser field numerically and analytically by using the time-dependent SchrSdinger equation. The broad rot...This paper studies the molecular rotational excitation and field-free spatial alignment in a nonresonant intense laser field numerically and analytically by using the time-dependent SchrSdinger equation. The broad rotational wave packets excited by the femtosecond pulse are defined in conjugate angle space, and their coefficients are obtained by solving a set of coupled linear equations. Both single molecule orientation angles and an ensemble of O2 and CO molecule angular distributions are calculated in detail. The numerical results show that, for single molecule highest occupied molecular orbital （HOMO） symmetry σ tends to have a molecular orientation along the laser polarization direction and the permanent dipole moment diminishes the mean of the orientation angles; for an ensemble of molecules, angular distributions provide more complex and additional information at times where there are no revivals in the single molecule plot. In particular, at the revival peak instant, with the increase of temperature of the molecular ensemble, the anisotropic angular distributions with respect to the laser polarization direction of the πg orbital gradually transform to the symmetrical distributions regarding the laser polarization vector and for two HOMO configurations angular distributions of all directions are confined within a smaller angle when the temperature of the molecular ensemble is higher.展开更多
Recently, there was a hot controversy about the concept of localized orbitals, which was triggered by Grushow＇s work titled ＂Is it time to retire the hybrid atomic orbital？＂ [J. Chem. Educ. 88, 860 （2011）]. To c...Recently, there was a hot controversy about the concept of localized orbitals, which was triggered by Grushow＇s work titled ＂Is it time to retire the hybrid atomic orbital？＂ [J. Chem. Educ. 88, 860 （2011）]. To clarify the issue, we assess the delocalized and localized molecular orbitals from an experimental view using electron momentum spectroscopy. The delocalized and localized molecular orbitals based on various theoretical models for CH4, NH3, and H20 are compared with the experimental momentum distributions. Our results show that the delocalized molecular orbitals rather than the localized ones can give a direct interpretation of the experimental （e, 2e） results.展开更多
The single ionization rate of the diatomic molecular ion H2^＋ with different active orbitals in an intense field is studied by using S-matrix theory. Our results show that the orientation-dependent single ionization ...The single ionization rate of the diatomic molecular ion H2^＋ with different active orbitals in an intense field is studied by using S-matrix theory. Our results show that the orientation-dependent single ionization probability of H2^＋ is greatly dependent on the symmetry and the electron density distribution of its initial states, and it can be used to identify the excited state of the molecular ion in the dissociation process.展开更多
The concept of resonance-assisted hydrogen bonds(RAHBs)highlights the synergistic interplay between theπ-resonance and hydrogen bonding interactions.This concept has been well-accepted in academia and is widely used ...The concept of resonance-assisted hydrogen bonds(RAHBs)highlights the synergistic interplay between theπ-resonance and hydrogen bonding interactions.This concept has been well-accepted in academia and is widely used in practice.However,it has been argued that the seemingly enhanced intramolecular hydrogen bonding(IMHB)in unsaturated compounds may simply be a result of the constraints imposed by theσ-skeleton framework.Thus,it is crucial to estimate the strength of IMHBs.In this work,we used two approaches to probe the resonance effect and estimate the strength of the IMHBs in the two exemplary cases of the enol forms of acetylacetone and o-hydroxyacetophenone.One approach is the block-localized wavefunction(BLW)method,which is a variant of the ab initio valence bond(VB)theory.Using this approach,it is possible to derive the geometries and energetics with resonance shut down.The other approach is Edmiston’s truncated localized molecular orbital(TLMO)technique,which monitors the energy changes by removing the delocalization tails from localized molecular orbitals.The integrated BLW and TLMO studies confirmed that the hydrogen bonding in these two molecules is indeed enhanced byπ-resonance,and that this enhancement is not a result ofσconstraints.展开更多
The highest occupied molecular orbital（HOMO） energies of fullerenes are found by quantitative first-principles calculations to be raised by negative charging, and the rising rate rank of the fullerenes is C60 >C7...The highest occupied molecular orbital（HOMO） energies of fullerenes are found by quantitative first-principles calculations to be raised by negative charging, and the rising rate rank of the fullerenes is C60 >C70 >C80 >C90>C100 >C180. Then we compare fullerenes with carbon nanotubes（CNTs） and graphene sheets（GSs） and find that the increase of the HOMO energy of a fullerene is much faster than that of CNTs and graphene sheets with the same number of C atoms. The rising rate rank is fullerene>CNT>GS, which holds no matter what the number of C atoms is or which structure the fullerene isomer is. This work paves a new path for developing all-carbon devices with low-dimensional carbon nanomaterials as different functional elements.展开更多
Carbon monosulfide molecular ion （CS＋）, which plays an important role in various research fields, has long been attracting much interest. Because of the unstable and transient nature of CS＋, its electronic states ...Carbon monosulfide molecular ion （CS＋）, which plays an important role in various research fields, has long been attracting much interest. Because of the unstable and transient nature of CS＋, its electronic states have not been well investigated. In this paper, the electronic states of CS＋ are studied by employing the internally contracted multireference configuration interaction method, and taking into account relativistic effects （scalar plus spin–orbit coupling）. The spin–orbit coupling effects are considered via the state-interacting method with the full Breit–Pauli Hamiltonian. The potential energy curves of 18 Λ–S states correlated with the two lowest dissociation limits of CS＋ molecular ion are calculated, and those of 10 lowest Ω states generated from the 6 lowest Λ–S states are also worked out. The spectroscopic constants of the bound states are evaluated, and they are in good agreement with available experimental results and theoretical values. With the aid of analysis of Λ–S composition of Ω states at different bond lengths, the avoided crossing phenomena in the electronic states of CS＋ are illuminated. Finally, the single ionization spectra of CS （X1Σ＋） populating the CS＋（X2Σ1/2＋, A2Π3/2, A2Π1/2, and B2Σ1/2＋） states are simulated. The vertical ionization potentials for X2Σ1/2＋, A2Π3/2, A2Π1/2, and B2Σ1/2＋ states are calculated to be 11.257, 12.787, 12.827, and 15.860 eV, respectively, which are accurate compared with previous experimental results, within an error margin of 0.08 eV^0.2 eV.展开更多
The electron excitation processes of H(1s)+He(1s^(2))→H(2s/2p)+He(1s^(2))are studied in impact energy range of 20-2000 e V/u by using the quantum-mechanical molecular orbital close-coupling(QMOCC)method.Total and sta...The electron excitation processes of H(1s)+He(1s^(2))→H(2s/2p)+He(1s^(2))are studied in impact energy range of 20-2000 e V/u by using the quantum-mechanical molecular orbital close-coupling(QMOCC)method.Total and state-selective cross sections have been obtained and compared with the available theoretical and experimental results.The results agree well with available measurements in the overlapping energy regions overall.The comparison of our results with other theoretical calculations further demonstrates the importance of considering a sufficient number of channels.The datasets presented in this paper,including the excitation cross sections,are openly available at https://www.doi.org/10.57760/sciencedb.j00113.00083.展开更多
Electron density distributions of 2-aminoethanol （2AE） and 2-amino-l-propanol （2AP） are calculated in both the coordinate and the momentum spaces using the B3LYP/TZVP method. Using the dual space analysis, molecul...Electron density distributions of 2-aminoethanol （2AE） and 2-amino-l-propanol （2AP） are calculated in both the coordinate and the momentum spaces using the B3LYP/TZVP method. Using the dual space analysis, molecular orbital signatures of the methyl substituent in 2AP are identified with respect to 2AE. Relaxations of the geometry and the valence orbital in 2AP are found to be due to the insertion of the methyl group. Five orbitals, not four orbitals, are identified as the methyl signatures. They are orbital 5a in the core shell, orbitals 9a and 10a in the inner valence shell, and orbitals 15a and 16a in the outer valence. In the inner valence shell, the attachment of methyl to 2AE causes a splitting of its orbital 8a into orbitals 9a and 10a of 2AP, whereas in the outer valence shell, the methyl group results in the insertion of an additional orbital pair of 15a and 16a. The frontier molecular orbitals 21a, 20a, and 19a are found to have no significant role in the methylation of 2AE.展开更多
基金supported by the Doctoral Research Fund of Henan Normal University,China (Grant No. 525449)
文摘This paper calculates the five most stable conformers of serine with Hartree-Fock theory, density functional theory （B3LYP）, Moller-Plesset perturbation theory （MP4（SDQ）） and electron propagation theory with the 6-311＋＋G（2d,2p） basis set. The calculated vertical ionization energies for the valence molecular orbitals of each conformer are in agreement with the experimental data, indicating that a range of molecular conformations would coexist in an equilibrium sample. Information of the five outer valence molecular orbitals for each conformer is explored in coordinate and momentum spaces using dual space analysis to investigate the conformational processes, which are generated from the global minimum conformer Serl by rotation of C2-C3 （Ser4）, C1 C2 （Ser5） and C1-O2 （Set2 and Ser3）. Orbitals 28a, 27a and 26a are identified as the fingerprint orbitals for all the conformational processes.
基金supported by the Program of Excellent Team in Harbin Institute of Technologythe Program for New Century Excellent Talents in University (NCET)National Natural Science Foundation of China (Grant Nos 10774033,60878018 and 10674036)
文摘This paper studies the molecular rotational excitation and field-free spatial alignment in a nonresonant intense laser field numerically and analytically by using the time-dependent SchrSdinger equation. The broad rotational wave packets excited by the femtosecond pulse are defined in conjugate angle space, and their coefficients are obtained by solving a set of coupled linear equations. Both single molecule orientation angles and an ensemble of O2 and CO molecule angular distributions are calculated in detail. The numerical results show that, for single molecule highest occupied molecular orbital （HOMO） symmetry σ tends to have a molecular orientation along the laser polarization direction and the permanent dipole moment diminishes the mean of the orientation angles; for an ensemble of molecules, angular distributions provide more complex and additional information at times where there are no revivals in the single molecule plot. In particular, at the revival peak instant, with the increase of temperature of the molecular ensemble, the anisotropic angular distributions with respect to the laser polarization direction of the πg orbital gradually transform to the symmetrical distributions regarding the laser polarization vector and for two HOMO configurations angular distributions of all directions are confined within a smaller angle when the temperature of the molecular ensemble is higher.
基金supported by the National Natural Science Foundation of China(Grant No.11174175)the Tsinghua University Initiative Scientific Research Program,China
文摘Recently, there was a hot controversy about the concept of localized orbitals, which was triggered by Grushow＇s work titled ＂Is it time to retire the hybrid atomic orbital？＂ [J. Chem. Educ. 88, 860 （2011）]. To clarify the issue, we assess the delocalized and localized molecular orbitals from an experimental view using electron momentum spectroscopy. The delocalized and localized molecular orbitals based on various theoretical models for CH4, NH3, and H20 are compared with the experimental momentum distributions. Our results show that the delocalized molecular orbitals rather than the localized ones can give a direct interpretation of the experimental （e, 2e） results.
基金Project supported by the National Natural Science Foundation of China (Grant No.10674087)the National Basic Research Program of China (Grant No.2006CB806000)+2 种基金the Hebei Provincial Natural Science Foundation (Grant No.A2008000136)the Project of National Center for Educational Techonology of the Ministry of Education of China (Grant NCET-08-0883)the Program of TYAl of Shanxi Province and China Academy of Engineering Physics Foundation (Grant No.2008B0102007)
文摘The single ionization rate of the diatomic molecular ion H2^＋ with different active orbitals in an intense field is studied by using S-matrix theory. Our results show that the orientation-dependent single ionization probability of H2^＋ is greatly dependent on the symmetry and the electron density distribution of its initial states, and it can be used to identify the excited state of the molecular ion in the dissociation process.
文摘The concept of resonance-assisted hydrogen bonds(RAHBs)highlights the synergistic interplay between theπ-resonance and hydrogen bonding interactions.This concept has been well-accepted in academia and is widely used in practice.However,it has been argued that the seemingly enhanced intramolecular hydrogen bonding(IMHB)in unsaturated compounds may simply be a result of the constraints imposed by theσ-skeleton framework.Thus,it is crucial to estimate the strength of IMHBs.In this work,we used two approaches to probe the resonance effect and estimate the strength of the IMHBs in the two exemplary cases of the enol forms of acetylacetone and o-hydroxyacetophenone.One approach is the block-localized wavefunction(BLW)method,which is a variant of the ab initio valence bond(VB)theory.Using this approach,it is possible to derive the geometries and energetics with resonance shut down.The other approach is Edmiston’s truncated localized molecular orbital(TLMO)technique,which monitors the energy changes by removing the delocalization tails from localized molecular orbitals.The integrated BLW and TLMO studies confirmed that the hydrogen bonding in these two molecules is indeed enhanced byπ-resonance,and that this enhancement is not a result ofσconstraints.
基金Supported by the National Natural Science Foundation of China under Grant Nos 11374174,51390471,51527803,and 51701143the National Basic Research Program of China under Grant No 2015CB654902+4 种基金the National Key Research and Development Program under Grant No 2016YFB0700402the Foundation for the Author of National Excellent Doctoral Dissertation under Grant No 201141the National Program for Thousand Young Talents of China,the Tianjin Municipal Education Commissionthe Tianjin Municipal Science and Technology Commissionthe Fundamental Research Fund of Tianjin University of Technology
文摘The highest occupied molecular orbital（HOMO） energies of fullerenes are found by quantitative first-principles calculations to be raised by negative charging, and the rising rate rank of the fullerenes is C60 >C70 >C80 >C90>C100 >C180. Then we compare fullerenes with carbon nanotubes（CNTs） and graphene sheets（GSs） and find that the increase of the HOMO energy of a fullerene is much faster than that of CNTs and graphene sheets with the same number of C atoms. The rising rate rank is fullerene>CNT>GS, which holds no matter what the number of C atoms is or which structure the fullerene isomer is. This work paves a new path for developing all-carbon devices with low-dimensional carbon nanomaterials as different functional elements.
基金Project supported by the National Basic Research Program of China(973 Program)(Grant No.2013CB922200)the National Natural Science Foundation of China(Grant Nos.11034003,11074095,and 11274140)+1 种基金the Natural Science Foundation of Heilongjiang Province,China(Grant No.QC2011C092)the Scientific Research Fund of Heilongjiang Provincial Education Department,China(Grant No.12531751)
文摘Carbon monosulfide molecular ion （CS＋）, which plays an important role in various research fields, has long been attracting much interest. Because of the unstable and transient nature of CS＋, its electronic states have not been well investigated. In this paper, the electronic states of CS＋ are studied by employing the internally contracted multireference configuration interaction method, and taking into account relativistic effects （scalar plus spin–orbit coupling）. The spin–orbit coupling effects are considered via the state-interacting method with the full Breit–Pauli Hamiltonian. The potential energy curves of 18 Λ–S states correlated with the two lowest dissociation limits of CS＋ molecular ion are calculated, and those of 10 lowest Ω states generated from the 6 lowest Λ–S states are also worked out. The spectroscopic constants of the bound states are evaluated, and they are in good agreement with available experimental results and theoretical values. With the aid of analysis of Λ–S composition of Ω states at different bond lengths, the avoided crossing phenomena in the electronic states of CS＋ are illuminated. Finally, the single ionization spectra of CS （X1Σ＋） populating the CS＋（X2Σ1/2＋, A2Π3/2, A2Π1/2, and B2Σ1/2＋） states are simulated. The vertical ionization potentials for X2Σ1/2＋, A2Π3/2, A2Π1/2, and B2Σ1/2＋ states are calculated to be 11.257, 12.787, 12.827, and 15.860 eV, respectively, which are accurate compared with previous experimental results, within an error margin of 0.08 eV^0.2 eV.
基金supported by the National Natural Science Foundation of China(Grant Nos.12204288,11934004,and 12274040)
文摘The electron excitation processes of H(1s)+He(1s^(2))→H(2s/2p)+He(1s^(2))are studied in impact energy range of 20-2000 e V/u by using the quantum-mechanical molecular orbital close-coupling(QMOCC)method.Total and state-selective cross sections have been obtained and compared with the available theoretical and experimental results.The results agree well with available measurements in the overlapping energy regions overall.The comparison of our results with other theoretical calculations further demonstrates the importance of considering a sufficient number of channels.The datasets presented in this paper,including the excitation cross sections,are openly available at https://www.doi.org/10.57760/sciencedb.j00113.00083.
基金Project supported by the Foundation of Henan Educational Committee, China (Grant No. 2011A140015)
文摘Electron density distributions of 2-aminoethanol （2AE） and 2-amino-l-propanol （2AP） are calculated in both the coordinate and the momentum spaces using the B3LYP/TZVP method. Using the dual space analysis, molecular orbital signatures of the methyl substituent in 2AP are identified with respect to 2AE. Relaxations of the geometry and the valence orbital in 2AP are found to be due to the insertion of the methyl group. Five orbitals, not four orbitals, are identified as the methyl signatures. They are orbital 5a in the core shell, orbitals 9a and 10a in the inner valence shell, and orbitals 15a and 16a in the outer valence. In the inner valence shell, the attachment of methyl to 2AE causes a splitting of its orbital 8a into orbitals 9a and 10a of 2AP, whereas in the outer valence shell, the methyl group results in the insertion of an additional orbital pair of 15a and 16a. The frontier molecular orbitals 21a, 20a, and 19a are found to have no significant role in the methylation of 2AE.
