A total of 45 alkylbenzenes were detected and identified in crude oils with different depositional environments and thermal maturities from the Tarim Basin,Beibuwan Basin,and Songliao Basin using comprehensive two-dim...A total of 45 alkylbenzenes were detected and identified in crude oils with different depositional environments and thermal maturities from the Tarim Basin,Beibuwan Basin,and Songliao Basin using comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry(GC×GCTOFMS).By analyzing the distribution characteristics of C0-C5alkylbenzenes,it is found that the content of some alkylbenzenes varies greatly in crude oils.Based on the distribution characteristics of 1,2,4,5-tetramethylbenzene(Te MB)and 1,2,3,4-Te MB,the ratio of 1,2,4,5-Te MB to 1,2,3,4-Te MB is proposed to indicate the organic matter origin and depositional environment of ancient sediments.Oil samples originated mainly from lower hydrobiont,algae,bacteria and source rocks deposited under reducing/anoxic conditions have low 1,2,4,5-/1,2,3,4-Te MB values(less than 0.6),while oil samples originated mainly from terrestrial higher plants and source rocks deposited under oxic/sub-oxic conditions have higher 1,2,4,5-/1,2,3,4-Te MB values(greater than 1.0).The significant difference of 1,2,4,5-/1,2,3,4-Te MB values is controlled by 1,2,4,5-Te MB content.1,2,4,5-Te MB content in oils derived from source rocks deposited in oxidized sedimentary environment(greater than 1.0 mg/g whole oil)is higher than that in oils from source rocks deposited in reduced sedimentary environment(less than 1.0 mg/g whole oil).1,2,4,5-/1,2,3,4-Te MB ratio might not or slightly be affected by evaporative fractionation,biodegradation and thermal maturity.1,2,4,5-/1,2,3,4-Te MB ratio and 1,2,4,5-Te MB content can be used as supplementary parameter for the identification of sedimentary environment and organic matter input.It should be noted that compared to the identification of organic matter sources,the 1,2,4,5-/1,2,3,4-Te MB parameter is more effective in identifying sedimentary environments.展开更多
Valence-bound molecular anions with polar neutral cores(μ>2.5 D)can support highly diffuse dipole-bound states(DBSs)as electronically excited states just below the detachment threshold.Such weakly bound nonvalence...Valence-bound molecular anions with polar neutral cores(μ>2.5 D)can support highly diffuse dipole-bound states(DBSs)as electronically excited states just below the detachment threshold.Such weakly bound nonvalence excited states have little influence on the structure of the neutral core,and they usually have the same vibrational frequencies.DBSs can be systematically searched using photodetachment spectroscopy(PDS),which can yield the binding energies of the DBSs,the electron detachment threshold of the anion,and above-threshold vibrational levels of the DBSs(Feshbach resonances).We have shown that the combination of PDS and resonant photoelectron spectroscopy(rPES)at the Feshbach resonances is a powerful approach to obtain rich vibrational information for complex molecular radicals.A prerequisite for this technique is to produce vibrationally cold anions,made possible by a cryogenically controlled Paul trap.In this article,we report a PDS and rPES study of cold para-ethylphenolate anions(p-EP^(-)).The electron affinity of the p-EP radical is measured to be 17425±3 cm^(-1)(2.1604±0.0004 eV),and a DBS is found at 145 cm^(-1) below the detachment threshold of p-EP^(-).Thirty-four vibrational levels are observed for the DBS,including two bound levels and 32 Feshbach resonances.Frequencies for 17 vibrational modes of the p-EP radical are measured from the combination of PDS and rPES,including six symmetry-forbidden modes with A″symmetry.The current study confirms again the power of combining cryogenic ion cooling with PDS and highresolution rPES to obtain spectroscopic information on complex molecular radicals.展开更多
The vacuum ultraviolet photodissociation of OCS via the F 3^1ΠRydberg states was investigated in the range of 134-140 nm by means of the time-sliced velocity map ion imaging technique.The images of S(^1D2)products fr...The vacuum ultraviolet photodissociation of OCS via the F 3^1ΠRydberg states was investigated in the range of 134-140 nm by means of the time-sliced velocity map ion imaging technique.The images of S(^1D2)products from the CO(X^1Σ^+)+S(^1D2)dissociation channel were acquired at five photolysis wavelengths,corresponding to a series of symmetric stretching vibrational excitations in OCS(F 3^1Π,v1=0-4).The total translational energy distributions,vibrational populations and angular distributions of CO(X^1Σ^+,v)coproducts were derived.The analysis of experimental results suggests that the excited OCS molecules dissociate to CO(X^1Σ^+)and S(^1D2)products via non-adiabatic couplings between the upper F 3^1Πstates and the lower-lying states both in the C∞v and Cs symmetry.Furthermore,strong wavelength dependent behavior has been observed:the greatly distinct vibrational populations and angular distributions of CO(X^1Σ^+,v)products from the lower(v1=0-2)and higher(v1=3,4)vibrational states of the excited OCS(F 3^1Π,v1)demonstrate that very different mechanisms are involved in the dissociation processes.This study provides evidence for the possible contribution of vibronic coupling and the crucial role of vibronic coupling on the vacuum ultraviolet photodissociation dynamics.展开更多
Here we report the study of the photodissociation dynamics of carbonyl sulfide in the vacuum ultraviolet region using the time-sliced velocity map ion imaging technique.Images of S(^3PJ=2,1,0),S(^1D2)and S(^1S0)produc...Here we report the study of the photodissociation dynamics of carbonyl sulfide in the vacuum ultraviolet region using the time-sliced velocity map ion imaging technique.Images of S(^3PJ=2,1,0),S(^1D2)and S(^1S0)products were measured at four photolysis wave-lengths of 129.32,128.14,126.99,and 126.08 nm,respectively.Four main dissociation channels:S(^3PJ=2,1,0)+CO(X^1Σ^+),S(^3PJ=2,1,0)+CO(A^3π),S(^1D2)+CO(X^1Σ^+)and S(^1S0)+CO(X^1Σ^+)channels,have been clearly observed and identified.Vibrational states of the CO co-products were partially resolved in the experimental images.From these images,the product total kinetic energy releases,the branching ratios and angular distributions of products have been derived.While the S(^3PJ=2,1,0)+CO(A^3π)product channel is formed through the adiabatic dissociation process after the excitation to the(3^1Σ^+)excited state,the results suggest that strong nonadiabatic coupling plays an important role in the formation of other three channels.展开更多
Vacuum ultraviolet photodissociation dynamics of N2O+hν→N2(X^(1)Σg+)+O(^(1)S0)in the short wavelength tail of D^(1)Σ+band has been investigated using the time-sliced velocity-mapped ion imaging technique by probin...Vacuum ultraviolet photodissociation dynamics of N2O+hν→N2(X^(1)Σg+)+O(^(1)S0)in the short wavelength tail of D^(1)Σ+band has been investigated using the time-sliced velocity-mapped ion imaging technique by probing the images of the O(^(1)S0)photoproducts at a set of photolysis wavelengths including 121.47 nm,122.17 nm,123.25 nm and 123.95 nm.The product total kinetic energy release distributions,vibrational state distributions of the N2(X^(1)Σg+)photofragments and angular anisotropy parameters have been obtained by analyzing the raw O(^(1)S0)images.It is noted that additional vibrationally excited photoproducts(3≤v≤8)with a Boltzmann-like feature start to appear except the non-statistical component as the photolysis wavelength decreases to 123.25 nm,and the corresponding populations become more pronounced with decreasing of the photolysis wavelength.Furthermore,the vibrational state specific anisotropy parameterβat each photolysis wavelength exhibits a drastic fluctuation nearβ=1.75 at v<8,and decreases to a minimum as the vibrational quantum number further increases.While the overall anisotropy parameterβfor the N2(X^(1)Σg+)+O(^(1)S0)channel presents a roughly monotonical increase from 1.63 at 121.47 nm to 1.95 at 123.95 nm.The experimental observations suggest that there is at least one fast nonadiabatic pathway from initially prepared D^(1)Σ+state to the dissociative state with bent geometry dominating to generate the additional vibrational structures at high photoexcitation energies.展开更多
The H+H2 reaction is the simplest chemical reaction system and has long been the prototype model in the study of reaction dynamics. Here we report a high resolution experimental investigation of the state-to-state rea...The H+H2 reaction is the simplest chemical reaction system and has long been the prototype model in the study of reaction dynamics. Here we report a high resolution experimental investigation of the state-to-state reaction dynamics in the H+HD→H2+D reaction by using the crossed molecular beams method and velocity map ion imaging technique at the collision energy of 1.17 eV. D atom products in this reaction were probed by the near threshold 1+1'(vacuum ultraviolet+ultraviolet) laser ionization scheme. The ion image with both high angular and energy resolution were acquired. State-to-state differential cross sections was accurately derived. Fast forward scattering oscillations, relating with interference effects in the scattering process, were clearly observed for H2 products at H2(v'=0,j'=1) and H2(v'=0,j'=3) rovibrational levels. This study further demonstrates the importance of measuring high-resolution differential cross sections in the study of state-to-state reaction dynamics in the gas phase.展开更多
基金supported by Doctor’s Scientific Research Initiation Project of Yan’an University(YAU202213093)National Natural Science Foundation of China(Grant No.41503029)。
文摘A total of 45 alkylbenzenes were detected and identified in crude oils with different depositional environments and thermal maturities from the Tarim Basin,Beibuwan Basin,and Songliao Basin using comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry(GC×GCTOFMS).By analyzing the distribution characteristics of C0-C5alkylbenzenes,it is found that the content of some alkylbenzenes varies greatly in crude oils.Based on the distribution characteristics of 1,2,4,5-tetramethylbenzene(Te MB)and 1,2,3,4-Te MB,the ratio of 1,2,4,5-Te MB to 1,2,3,4-Te MB is proposed to indicate the organic matter origin and depositional environment of ancient sediments.Oil samples originated mainly from lower hydrobiont,algae,bacteria and source rocks deposited under reducing/anoxic conditions have low 1,2,4,5-/1,2,3,4-Te MB values(less than 0.6),while oil samples originated mainly from terrestrial higher plants and source rocks deposited under oxic/sub-oxic conditions have higher 1,2,4,5-/1,2,3,4-Te MB values(greater than 1.0).The significant difference of 1,2,4,5-/1,2,3,4-Te MB values is controlled by 1,2,4,5-Te MB content.1,2,4,5-Te MB content in oils derived from source rocks deposited in oxidized sedimentary environment(greater than 1.0 mg/g whole oil)is higher than that in oils from source rocks deposited in reduced sedimentary environment(less than 1.0 mg/g whole oil).1,2,4,5-/1,2,3,4-Te MB ratio might not or slightly be affected by evaporative fractionation,biodegradation and thermal maturity.1,2,4,5-/1,2,3,4-Te MB ratio and 1,2,4,5-Te MB content can be used as supplementary parameter for the identification of sedimentary environment and organic matter input.It should be noted that compared to the identification of organic matter sources,the 1,2,4,5-/1,2,3,4-Te MB parameter is more effective in identifying sedimentary environments.
基金supported by the Department of Energy,Office of Basic Energy Sciences,Chemical Sciences,Geosciences,and Biosciences Division under Grant DE-SC0018679.
文摘Valence-bound molecular anions with polar neutral cores(μ>2.5 D)can support highly diffuse dipole-bound states(DBSs)as electronically excited states just below the detachment threshold.Such weakly bound nonvalence excited states have little influence on the structure of the neutral core,and they usually have the same vibrational frequencies.DBSs can be systematically searched using photodetachment spectroscopy(PDS),which can yield the binding energies of the DBSs,the electron detachment threshold of the anion,and above-threshold vibrational levels of the DBSs(Feshbach resonances).We have shown that the combination of PDS and resonant photoelectron spectroscopy(rPES)at the Feshbach resonances is a powerful approach to obtain rich vibrational information for complex molecular radicals.A prerequisite for this technique is to produce vibrationally cold anions,made possible by a cryogenically controlled Paul trap.In this article,we report a PDS and rPES study of cold para-ethylphenolate anions(p-EP^(-)).The electron affinity of the p-EP radical is measured to be 17425±3 cm^(-1)(2.1604±0.0004 eV),and a DBS is found at 145 cm^(-1) below the detachment threshold of p-EP^(-).Thirty-four vibrational levels are observed for the DBS,including two bound levels and 32 Feshbach resonances.Frequencies for 17 vibrational modes of the p-EP radical are measured from the combination of PDS and rPES,including six symmetry-forbidden modes with A″symmetry.The current study confirms again the power of combining cryogenic ion cooling with PDS and highresolution rPES to obtain spectroscopic information on complex molecular radicals.
基金supported by the National Key R&D Program of China(No.2017YFF0104500)the National Natural Science Foundation of China(No.21473173,No.21590802,No.21673216,and No.21773213)the Strategic Priority Research Program of Chinese Academy of Sciences(No.XDB17000000).
文摘The vacuum ultraviolet photodissociation of OCS via the F 3^1ΠRydberg states was investigated in the range of 134-140 nm by means of the time-sliced velocity map ion imaging technique.The images of S(^1D2)products from the CO(X^1Σ^+)+S(^1D2)dissociation channel were acquired at five photolysis wavelengths,corresponding to a series of symmetric stretching vibrational excitations in OCS(F 3^1Π,v1=0-4).The total translational energy distributions,vibrational populations and angular distributions of CO(X^1Σ^+,v)coproducts were derived.The analysis of experimental results suggests that the excited OCS molecules dissociate to CO(X^1Σ^+)and S(^1D2)products via non-adiabatic couplings between the upper F 3^1Πstates and the lower-lying states both in the C∞v and Cs symmetry.Furthermore,strong wavelength dependent behavior has been observed:the greatly distinct vibrational populations and angular distributions of CO(X^1Σ^+,v)products from the lower(v1=0-2)and higher(v1=3,4)vibrational states of the excited OCS(F 3^1Π,v1)demonstrate that very different mechanisms are involved in the dissociation processes.This study provides evidence for the possible contribution of vibronic coupling and the crucial role of vibronic coupling on the vacuum ultraviolet photodissociation dynamics.
基金supported by the National Key R&D Program of China (No.2016YFF0200500)the National Natural Science Foundation of China (No.21473173,No.21590802,No.21327901 and No.21773213)+1 种基金the Strategic Priority Research Program of Chinese Academy of Sciences (No.XDB17000000)the Fundamental Research Funds for the Central Universities.
文摘Here we report the study of the photodissociation dynamics of carbonyl sulfide in the vacuum ultraviolet region using the time-sliced velocity map ion imaging technique.Images of S(^3PJ=2,1,0),S(^1D2)and S(^1S0)products were measured at four photolysis wave-lengths of 129.32,128.14,126.99,and 126.08 nm,respectively.Four main dissociation channels:S(^3PJ=2,1,0)+CO(X^1Σ^+),S(^3PJ=2,1,0)+CO(A^3π),S(^1D2)+CO(X^1Σ^+)and S(^1S0)+CO(X^1Σ^+)channels,have been clearly observed and identified.Vibrational states of the CO co-products were partially resolved in the experimental images.From these images,the product total kinetic energy releases,the branching ratios and angular distributions of products have been derived.While the S(^3PJ=2,1,0)+CO(A^3π)product channel is formed through the adiabatic dissociation process after the excitation to the(3^1Σ^+)excited state,the results suggest that strong nonadiabatic coupling plays an important role in the formation of other three channels.
基金supported by the National Natural Science Foundation of China(No.21773213)。
文摘Vacuum ultraviolet photodissociation dynamics of N2O+hν→N2(X^(1)Σg+)+O(^(1)S0)in the short wavelength tail of D^(1)Σ+band has been investigated using the time-sliced velocity-mapped ion imaging technique by probing the images of the O(^(1)S0)photoproducts at a set of photolysis wavelengths including 121.47 nm,122.17 nm,123.25 nm and 123.95 nm.The product total kinetic energy release distributions,vibrational state distributions of the N2(X^(1)Σg+)photofragments and angular anisotropy parameters have been obtained by analyzing the raw O(^(1)S0)images.It is noted that additional vibrationally excited photoproducts(3≤v≤8)with a Boltzmann-like feature start to appear except the non-statistical component as the photolysis wavelength decreases to 123.25 nm,and the corresponding populations become more pronounced with decreasing of the photolysis wavelength.Furthermore,the vibrational state specific anisotropy parameterβat each photolysis wavelength exhibits a drastic fluctuation nearβ=1.75 at v<8,and decreases to a minimum as the vibrational quantum number further increases.While the overall anisotropy parameterβfor the N2(X^(1)Σg+)+O(^(1)S0)channel presents a roughly monotonical increase from 1.63 at 121.47 nm to 1.95 at 123.95 nm.The experimental observations suggest that there is at least one fast nonadiabatic pathway from initially prepared D^(1)Σ+state to the dissociative state with bent geometry dominating to generate the additional vibrational structures at high photoexcitation energies.
基金supported by the National Key R&D Program of China (No.2016YFF0200500)the National Natural Science Foundation of China (No.21473173, No.21590802, No.21403207, No.21503206)the Strategic Priority Research Program of Chinese Academy of Sciences (No.XDB17000000)
文摘The H+H2 reaction is the simplest chemical reaction system and has long been the prototype model in the study of reaction dynamics. Here we report a high resolution experimental investigation of the state-to-state reaction dynamics in the H+HD→H2+D reaction by using the crossed molecular beams method and velocity map ion imaging technique at the collision energy of 1.17 eV. D atom products in this reaction were probed by the near threshold 1+1'(vacuum ultraviolet+ultraviolet) laser ionization scheme. The ion image with both high angular and energy resolution were acquired. State-to-state differential cross sections was accurately derived. Fast forward scattering oscillations, relating with interference effects in the scattering process, were clearly observed for H2 products at H2(v'=0,j'=1) and H2(v'=0,j'=3) rovibrational levels. This study further demonstrates the importance of measuring high-resolution differential cross sections in the study of state-to-state reaction dynamics in the gas phase.
