A graphically oriented interactive program for assignments of rotationally resolved molecular spectra has been devised. The program functions by grouping spectral lines in term of the second difference principle. and ...A graphically oriented interactive program for assignments of rotationally resolved molecular spectra has been devised. The program functions by grouping spectral lines in term of the second difference principle. and graphing spectral intensity versus frequency in a bar graph of the selected groups, distinguished by color and/or line-type. This allows for easy detection of regular patterns buried in the observed spectrum. Furthermore, it includes a Loomis-Wood view for assisting in spectral assignments. As an example, the program was applied in assigning the molecular spectrum of the production in the discharge of PCl3 buffered by helium gas, which may belong to several species. The results suggest that the program is highly efficient and quite useful in the assignment and the analysis of molecular spectra, especially those of symmetric top, slightly asymmetric top and linear molecules. The accuracy and efficiency of this program will likely ensure its wide application in the processing of molecular spectra.展开更多
Time-integrated optical emission analysis of laser-induced plasma on Teflon is presented.Plasma was induced under atmospheric pressure air using transversely excited atmospheric CO_(2) laser pulses.Teflon is a C-based...Time-integrated optical emission analysis of laser-induced plasma on Teflon is presented.Plasma was induced under atmospheric pressure air using transversely excited atmospheric CO_(2) laser pulses.Teflon is a C-based polymer that is,among other things,interesting as a substrate for laser-induced breakdown spectroscopy analysis of liquid samples.This study aimed to determine the optimal experimental conditions for obtaining neutral and ionized C spectral lines and C2 and CN molecular band emission suitable for spectrochemical purposes.Evaluation of plasma parameters was done using several spectroscopic techniques.Stark profiles of appropriate C ionic lines were used to determine electron number density.The ratio of the integral intensity of ionic-to-atomic C spectral lines was used to determine the ionization temperature.A spectral emission of C2 Swan and CN violet bands system was used to determine the temperature of the colder,peripheral parts of plasma.We critically analyzed the use of molecular emission bands as a tool for plasma diagnostics and suggested methods for possible improvements.展开更多
Equilibrium structures and infrared spectra of four typical molecular models of coal have been studied by density functional calculations. Combining theoretical calculations on the coal models with experimental FT-IR ...Equilibrium structures and infrared spectra of four typical molecular models of coal have been studied by density functional calculations. Combining theoretical calculations on the coal models with experimental FT-IR spectra of selected low rank perhydrous coals, a plausible molecular representation for this kind of coals was proposed, and its predicted IR spectra reasonably match the experimental observation. Calculations indicate that the cleavage of the C-C bridge bond for the coal structures considered here occurs at about 540 ℃ and the C-O ether bridge bond may break under temperature ranging from 500 to 600 ℃for the aryl-CH2-O-CH2-aryl ether bond or from 200 to 300 ℃ for the aryl-CH2-O-aryl ether bond, showing remarkable effect of the local structural environment. The coal model containing the carboxyl group may release CO2 at about 300 ℃ through the decarboxylation with a barrier of 69 kcal/mol.展开更多
Dual-comb spectrometry suffers the fluctuations of parameters in combs. We demonstrate that the repetition rate is more important than any other parameter, since the fluctuation of the repetition rate leads to a chang...Dual-comb spectrometry suffers the fluctuations of parameters in combs. We demonstrate that the repetition rate is more important than any other parameter, since the fluctuation of the repetition rate leads to a change of difference in the repetition rate between both combs, consequently causing the conversion factor variation and spectral frequency misalignment. The measured frequency noise power spectral density of the repetition rate exhibits an integrated residual frequency modulation of 1.4 Hz from 1 Hz to 100 kHz in our system. This value corresponds to the absorption peak fluctuation within a root mean square value of 0.19 cm-1 that is verified by both simulation and experimental result. Further, we can also simulate spectrum degradation as the fluctuation varies. After modifying misaligned sPectra and averaging, the measured result agrees well with the simulated spectrum based on the GEISA database.展开更多
Theoretical study on coordinates between crown ethers and aniline as well as monosaccharides is performed by AM1, MNDO and PM3 methods. It is indicated that crown ethers possess ability to recognize polar guests espec...Theoretical study on coordinates between crown ethers and aniline as well as monosaccharides is performed by AM1, MNDO and PM3 methods. It is indicated that crown ethers possess ability to recognize polar guests especially ionic guests and monosaccharides. Electronic spectra of coordinates are computed by the INDO/SCI method. The reason of the blue-shift for UV absorption of complexes relative to that of hosts is discussed and electronic transition is theoretic- cally assigned.展开更多
The optimized molecular structures and vibrational frequencies of 4-mercaptopyridine（4MPY） monomer and its dihydrate were studied by means of the density functional theory（ DFT）, viz. B3LYP method with the 6-311 ...The optimized molecular structures and vibrational frequencies of 4-mercaptopyridine（4MPY） monomer and its dihydrate were studied by means of the density functional theory（ DFT）, viz. B3LYP method with the 6-311 ＋ ＋ G （d,p） basis set. On the basis of the calculations, the assignments of the vibrational spectra of the monomer and the dihydrate were performed, and so were investigated the changes in the structure and the vibrational spectrum of the di- hydrate as well as the intermolecular force resulting in the formation of the dihydrate. The calculated results show that each of the water molecule planes is vertical to the pyridine ring plane in the dihydrate that is formed via the H-bonds between 4MPY and water molecules. Furthermore, the structure and the vibrational spectrum of 4MPY can be considerably affected by the water molecules.展开更多
Atomic and molecular processes relevant to the volumetric recombinationphenomena were investigated in a linear divertor plasma simulator MAP-Ⅱ. Volumetric recombinationis induced in He plasma by puffing of He or H_2....Atomic and molecular processes relevant to the volumetric recombinationphenomena were investigated in a linear divertor plasma simulator MAP-Ⅱ. Volumetric recombinationis induced in He plasma by puffing of He or H_2. In the He puffing case, the reduction of the ionflux is dominated by the electron-ion recombination. In the H_2 puffing case, however, it isdominated by the molecule-assisted recombination (MAR), which is characterized by the disappearanceof the Helium Rydberg spectra and by the existence of the hydrogen negative ions. Currentachievement and the future prospect are described.展开更多
All-atom molecular dynamic simulations and 2D-NOESY spectra were used to study the conformations and hydrogen bonds of ACE inhibitory tripeptide Ile-Ile-Pro(IIP) in aqueous and DMSO solutions. RMSD, Dis, Rg and SASA w...All-atom molecular dynamic simulations and 2D-NOESY spectra were used to study the conformations and hydrogen bonds of ACE inhibitory tripeptide Ile-Ile-Pro(IIP) in aqueous and DMSO solutions. RMSD, Dis, Rg and SASA were adopted to characterize the properties of tripeptide Ile-Ile-Pro in the MD simulations. Interestingly, the tripeptide molecule IIP exhibited different behaviors in aqueous and DMSO solutions. In aqueous solution, IIP was very flexible. The conformation could shift between extended and folded states very quickly. However,in DMSO solution, more folded conformations were observed. The interesting phenomena were proved by 2D-NOESY spectra.展开更多
^(13)C-NMR ~1H-decoupled spectra of styrene polymers were assigned by comparison with modelcompounds, then used in measurements of number average molecular weights. The higher limit of an exactdetermination of the end...^(13)C-NMR ~1H-decoupled spectra of styrene polymers were assigned by comparison with modelcompounds, then used in measurements of number average molecular weights. The higher limit of an exactdetermination of the end group signal is less than a molecular weight of 10~4. For polymer samples withM_n<10~3, the results obtained from ^(13)C-NMR spectra of saturated carbon region are in excellent agreementwith the values determined by ~1H-NMR, SEC, and VPO methods, while the results from ^(13)C-NMR spectra ofphenyl C-1 carbon region are somewhat higher than the values determined by other methods.展开更多
苯(C 6 H 6)作为大气和室内环境中的主要污染物,具有强烈致癌性,是大气环境主要监测的内容之一。基于群论方法分析建立一种苯分子的泛频跃迁谱线计算方法,利用苯分子简正振动模式与光谱活性,获得30个振动模式的振动频率及其不可约表示...苯(C 6 H 6)作为大气和室内环境中的主要污染物,具有强烈致癌性,是大气环境主要监测的内容之一。基于群论方法分析建立一种苯分子的泛频跃迁谱线计算方法,利用苯分子简正振动模式与光谱活性,获得30个振动模式的振动频率及其不可约表示。基于D 6点群乘法规则,给出苯分子泛频跃迁的振动模式、光谱活性与谱线位置,为后续精确测量近红外区域苯分子未知谱线跃迁提供了数据与理论支撑。展开更多
基金This work was supported by the National Natural Science Foundation of China （NSFC No.10574045 and No.10434060）and Science and Technology Commission of Shanghai Municipality（No.04DZ14009）.The authors are grateful to Hua-huiZhu for his valuable suggestions.
文摘A graphically oriented interactive program for assignments of rotationally resolved molecular spectra has been devised. The program functions by grouping spectral lines in term of the second difference principle. and graphing spectral intensity versus frequency in a bar graph of the selected groups, distinguished by color and/or line-type. This allows for easy detection of regular patterns buried in the observed spectrum. Furthermore, it includes a Loomis-Wood view for assisting in spectral assignments. As an example, the program was applied in assigning the molecular spectrum of the production in the discharge of PCl3 buffered by helium gas, which may belong to several species. The results suggest that the program is highly efficient and quite useful in the assignment and the analysis of molecular spectra, especially those of symmetric top, slightly asymmetric top and linear molecules. The accuracy and efficiency of this program will likely ensure its wide application in the processing of molecular spectra.
基金funded by the Ministry of Education,Science and Technological Development of the Republic of Serbia(Nos.451-03-68/2022-14/200017 and 451-03-68/2022-14/200146)the financial support of the State Committee on Science and Technology of the Republic of Belarusthe Belarusian Republican Foundation for Fundamental Research(No.F20SRBG-001)。
文摘Time-integrated optical emission analysis of laser-induced plasma on Teflon is presented.Plasma was induced under atmospheric pressure air using transversely excited atmospheric CO_(2) laser pulses.Teflon is a C-based polymer that is,among other things,interesting as a substrate for laser-induced breakdown spectroscopy analysis of liquid samples.This study aimed to determine the optimal experimental conditions for obtaining neutral and ionized C spectral lines and C2 and CN molecular band emission suitable for spectrochemical purposes.Evaluation of plasma parameters was done using several spectroscopic techniques.Stark profiles of appropriate C ionic lines were used to determine electron number density.The ratio of the integral intensity of ionic-to-atomic C spectral lines was used to determine the ionization temperature.A spectral emission of C2 Swan and CN violet bands system was used to determine the temperature of the colder,peripheral parts of plasma.We critically analyzed the use of molecular emission bands as a tool for plasma diagnostics and suggested methods for possible improvements.
基金supported by the Ministry of Science and Technology (2012CB214900 and 2011CB808504)the National Science Foundation of China (21133007)
文摘Equilibrium structures and infrared spectra of four typical molecular models of coal have been studied by density functional calculations. Combining theoretical calculations on the coal models with experimental FT-IR spectra of selected low rank perhydrous coals, a plausible molecular representation for this kind of coals was proposed, and its predicted IR spectra reasonably match the experimental observation. Calculations indicate that the cleavage of the C-C bridge bond for the coal structures considered here occurs at about 540 ℃ and the C-O ether bridge bond may break under temperature ranging from 500 to 600 ℃for the aryl-CH2-O-CH2-aryl ether bond or from 200 to 300 ℃ for the aryl-CH2-O-aryl ether bond, showing remarkable effect of the local structural environment. The coal model containing the carboxyl group may release CO2 at about 300 ℃ through the decarboxylation with a barrier of 69 kcal/mol.
基金supported by the State Key Laboratory of Precision Measurement Technology & Instruments of Tsinghua University and the Young Scientists Fund of the National Natural Science Foundation of China(Grant No.61205147)
文摘Dual-comb spectrometry suffers the fluctuations of parameters in combs. We demonstrate that the repetition rate is more important than any other parameter, since the fluctuation of the repetition rate leads to a change of difference in the repetition rate between both combs, consequently causing the conversion factor variation and spectral frequency misalignment. The measured frequency noise power spectral density of the repetition rate exhibits an integrated residual frequency modulation of 1.4 Hz from 1 Hz to 100 kHz in our system. This value corresponds to the absorption peak fluctuation within a root mean square value of 0.19 cm-1 that is verified by both simulation and experimental result. Further, we can also simulate spectrum degradation as the fluctuation varies. After modifying misaligned sPectra and averaging, the measured result agrees well with the simulated spectrum based on the GEISA database.
文摘Theoretical study on coordinates between crown ethers and aniline as well as monosaccharides is performed by AM1, MNDO and PM3 methods. It is indicated that crown ethers possess ability to recognize polar guests especially ionic guests and monosaccharides. Electronic spectra of coordinates are computed by the INDO/SCI method. The reason of the blue-shift for UV absorption of complexes relative to that of hosts is discussed and electronic transition is theoretic- cally assigned.
文摘The optimized molecular structures and vibrational frequencies of 4-mercaptopyridine（4MPY） monomer and its dihydrate were studied by means of the density functional theory（ DFT）, viz. B3LYP method with the 6-311 ＋ ＋ G （d,p） basis set. On the basis of the calculations, the assignments of the vibrational spectra of the monomer and the dihydrate were performed, and so were investigated the changes in the structure and the vibrational spectrum of the di- hydrate as well as the intermolecular force resulting in the formation of the dihydrate. The calculated results show that each of the water molecule planes is vertical to the pyridine ring plane in the dihydrate that is formed via the H-bonds between 4MPY and water molecules. Furthermore, the structure and the vibrational spectrum of 4MPY can be considerably affected by the water molecules.
基金The project partly supported by TEPCO Research Foundation
文摘Atomic and molecular processes relevant to the volumetric recombinationphenomena were investigated in a linear divertor plasma simulator MAP-Ⅱ. Volumetric recombinationis induced in He plasma by puffing of He or H_2. In the He puffing case, the reduction of the ionflux is dominated by the electron-ion recombination. In the H_2 puffing case, however, it isdominated by the molecule-assisted recombination (MAR), which is characterized by the disappearanceof the Helium Rydberg spectra and by the existence of the hydrogen negative ions. Currentachievement and the future prospect are described.
基金Supported by the National Natural Science Foundation of China(No.20903026)the Talents Introduction Foundation for Universities of Guangdong Province(2011)Scientific Research Foundation of the Natural Science Foundation of Guangdong Province(No.S2011010002483)
文摘All-atom molecular dynamic simulations and 2D-NOESY spectra were used to study the conformations and hydrogen bonds of ACE inhibitory tripeptide Ile-Ile-Pro(IIP) in aqueous and DMSO solutions. RMSD, Dis, Rg and SASA were adopted to characterize the properties of tripeptide Ile-Ile-Pro in the MD simulations. Interestingly, the tripeptide molecule IIP exhibited different behaviors in aqueous and DMSO solutions. In aqueous solution, IIP was very flexible. The conformation could shift between extended and folded states very quickly. However,in DMSO solution, more folded conformations were observed. The interesting phenomena were proved by 2D-NOESY spectra.
基金The Project is supported by the Chinese National Basic Research Project"Macromolecular Condensed State"and the National Natural Science Foundation of China.
文摘^(13)C-NMR ~1H-decoupled spectra of styrene polymers were assigned by comparison with modelcompounds, then used in measurements of number average molecular weights. The higher limit of an exactdetermination of the end group signal is less than a molecular weight of 10~4. For polymer samples withM_n<10~3, the results obtained from ^(13)C-NMR spectra of saturated carbon region are in excellent agreementwith the values determined by ~1H-NMR, SEC, and VPO methods, while the results from ^(13)C-NMR spectra ofphenyl C-1 carbon region are somewhat higher than the values determined by other methods.
文摘苯(C 6 H 6)作为大气和室内环境中的主要污染物,具有强烈致癌性,是大气环境主要监测的内容之一。基于群论方法分析建立一种苯分子的泛频跃迁谱线计算方法,利用苯分子简正振动模式与光谱活性,获得30个振动模式的振动频率及其不可约表示。基于D 6点群乘法规则,给出苯分子泛频跃迁的振动模式、光谱活性与谱线位置,为后续精确测量近红外区域苯分子未知谱线跃迁提供了数据与理论支撑。
