A two-channel thermal dissociation cavity ring down spectroscopy (CRDS) instrument has been built for in situ, real-time measurement of NO2 and total RNO2 (peroxy nitrates and alkyl nitrates) in ambient air, with ...A two-channel thermal dissociation cavity ring down spectroscopy (CRDS) instrument has been built for in situ, real-time measurement of NO2 and total RNO2 (peroxy nitrates and alkyl nitrates) in ambient air, with a NO2 detection limit of 0.10 ppbv at 1 s. A 6-day long measurement was conducted at urban site of Hefei by using the CRDS instrument with a time resolution of 3 s. A commercial molybdenum converted chemiluminescence (Mo-CL) instrument was also used for comparison. The average RNO2 concentration in the 6 days was measured to be 1.94 ppbv. The Mo-CL instrument overestimated the NO2 concentration by a bias of +1.69 ppbv in average, for the reason that it cannot distinguish RNO2 from NO2. The relative bias could be over 100% during the afternoon hours when NO2 was low but RNO2 was high.展开更多
Metastable 40Ar* atoms are produced in the two metastable states 3p54s [3/2]2 and 3p5 4s′ [1/2]0 in a pulsed DC discharge in a beam, and are subsequently excited to the even-parity autoionizing resonance series 3pSn...Metastable 40Ar* atoms are produced in the two metastable states 3p54s [3/2]2 and 3p5 4s′ [1/2]0 in a pulsed DC discharge in a beam, and are subsequently excited to the even-parity autoionizing resonance series 3pSnp′[3/2]1,2, 3p5 np′ [1/2]1, and 3p5nf′[5/2]3 using single photon excitation with a pulsed dye laser. The excitation spectra of the even-parity autoion- izing resonance series from the metastable 40Ar* are obtained by recording the autoionized Ar+ ions with time-of-flight ion detection in the photon energy range of 32500-35600 cm-1 with an experimental bandwidth of 〈0.1 cm-1. A wealth of autoionizing resonances are newly observed, from which more precise and systematic spectroscopic data of the level energies and quantum defects are derived.展开更多
The H atom production channels in the ultraviolet (UV) photochemistry of m-pyridyl radical (m-C5H4N) were investigated at excitation wavelengths from 224 nm to 248 nm by high-n Rydberg atom time-of-flight (HRTOF...The H atom production channels in the ultraviolet (UV) photochemistry of m-pyridyl radical (m-C5H4N) were investigated at excitation wavelengths from 224 nm to 248 nm by high-n Rydberg atom time-of-flight (HRTOF) technique. The photofragment yield (PFY) spectrum of the H atoms indicates a broad UV absorption feature near 234 nm. The product kinetic energy release is small; the average product kinetic energy at the wavelengths from 224 nm to 248 nm is 0.12 to 0.19 of the maximum excess energy (assuming the lowest energy product channel, H+cyanovinylacetylene). The product kinetic energy distributions are consistent with the H cyanovinylacetylene, H 3,4-pyridyne, and H 2,3-pyridyne product channels, with H cyanovinylacetylene as the main H-loss channel. The angular distributions of the H-atom products are isotropic. After the UV electronic excitation, the m-pyridyl radical undergoes internal conversion to the ground electronic state and then unimolecular dissoci-ation to the H cyanovinylacetylene, H 3,4-pyridyne, and H 2,3-pyridyne products. The dissociation mechanism of the m-pyridyl radical is similar to that of the o-pyridyl radical reported in the early study.展开更多
The ultraviolet (UV) photodissociation of jet-cooled 1-pentyl radical is investigated in the wavelength region of 236-254 nm using the high-n Rydberg-atom time-of-flight (HRTOF) technique. The H-atom photofragment...The ultraviolet (UV) photodissociation of jet-cooled 1-pentyl radical is investigated in the wavelength region of 236-254 nm using the high-n Rydberg-atom time-of-flight (HRTOF) technique. The H-atom photofragment yield spectrum of the 1-pentyl radical shows a broad UV absorption feature peaking near 245 nm, similar to the 2pz→3s absorption bands of ethyl and n-propyl. The center-of-mass translational energy distribution, P(ET), of the H+CsH10 product channel is bimodal, with a slow peak at -5 kcal/mol and a fast peak at -50 kcal/mol. The fraction of the average translational energy release in the total available energy, (fT), is 0.30, with those of the slow and fast components being 0.13 and 0.58, respectively. The slow component has an isotropic product angular distribution, while the fast component is anisotropic with an anisotropy parameter -0.4. The bimodal translational energy and angular distributions of the H+C5H10 products indicate two H-atom elimination channels in the photodissociation of 1-pentyl: (i) a direct, prompt dissociation from the electronic excited state and/or the repulsive part of the ground electronic state potential energy surface; and (ii) a unimolecular dissociation of internally hot radical in the ground electronic state after internal conversion from the electronic excited state.展开更多
Two-photon dissociation dynamics of the OH radical is studied using the high-n Rydberg atom time-of-flight(HRTOF) technique. The H(2 S)+O(1 D) and H(2 S)+O(1 S) product channels are observed in the dissociation of the...Two-photon dissociation dynamics of the OH radical is studied using the high-n Rydberg atom time-of-flight(HRTOF) technique. The H(2 S)+O(1 D) and H(2 S)+O(1 S) product channels are observed in the dissociation of the OH radical on the 22Π and B2Σ+repulsive states, respectively, from sequential two-photon excitation via the A2Σ+(v′=2, J′=0.5-2.5)state. Both H+O product channels have anisotropic angular distributions, with β=-0.97 for H(2 S)+O(1 D) and 1.97 for H(2 S)+O(1 S). The anisotropic angular distributions are consistent with a mechanism of OH direct dissociation on the repulsive potential energy curves(PECs) leading to the H+O products. The OH bond dissociation energy D0(O-H) is determined to be 35580±15 cm-1.展开更多
文摘A two-channel thermal dissociation cavity ring down spectroscopy (CRDS) instrument has been built for in situ, real-time measurement of NO2 and total RNO2 (peroxy nitrates and alkyl nitrates) in ambient air, with a NO2 detection limit of 0.10 ppbv at 1 s. A 6-day long measurement was conducted at urban site of Hefei by using the CRDS instrument with a time resolution of 3 s. A commercial molybdenum converted chemiluminescence (Mo-CL) instrument was also used for comparison. The average RNO2 concentration in the 6 days was measured to be 1.94 ppbv. The Mo-CL instrument overestimated the NO2 concentration by a bias of +1.69 ppbv in average, for the reason that it cannot distinguish RNO2 from NO2. The relative bias could be over 100% during the afternoon hours when NO2 was low but RNO2 was high.
文摘Metastable 40Ar* atoms are produced in the two metastable states 3p54s [3/2]2 and 3p5 4s′ [1/2]0 in a pulsed DC discharge in a beam, and are subsequently excited to the even-parity autoionizing resonance series 3pSnp′[3/2]1,2, 3p5 np′ [1/2]1, and 3p5nf′[5/2]3 using single photon excitation with a pulsed dye laser. The excitation spectra of the even-parity autoion- izing resonance series from the metastable 40Ar* are obtained by recording the autoionized Ar+ ions with time-of-flight ion detection in the photon energy range of 32500-35600 cm-1 with an experimental bandwidth of 〈0.1 cm-1. A wealth of autoionizing resonances are newly observed, from which more precise and systematic spectroscopic data of the level energies and quantum defects are derived.
基金This work was supported by the US National Science Foundation (CHE-1214157). Jasmine Minor acknowledges the support from the UC Riverside HSI-STEM Summer Bridge to Research Program and the Summer Research in Science and Engineering [RISE] Program.
文摘The H atom production channels in the ultraviolet (UV) photochemistry of m-pyridyl radical (m-C5H4N) were investigated at excitation wavelengths from 224 nm to 248 nm by high-n Rydberg atom time-of-flight (HRTOF) technique. The photofragment yield (PFY) spectrum of the H atoms indicates a broad UV absorption feature near 234 nm. The product kinetic energy release is small; the average product kinetic energy at the wavelengths from 224 nm to 248 nm is 0.12 to 0.19 of the maximum excess energy (assuming the lowest energy product channel, H+cyanovinylacetylene). The product kinetic energy distributions are consistent with the H cyanovinylacetylene, H 3,4-pyridyne, and H 2,3-pyridyne product channels, with H cyanovinylacetylene as the main H-loss channel. The angular distributions of the H-atom products are isotropic. After the UV electronic excitation, the m-pyridyl radical undergoes internal conversion to the ground electronic state and then unimolecular dissoci-ation to the H cyanovinylacetylene, H 3,4-pyridyne, and H 2,3-pyridyne products. The dissociation mechanism of the m-pyridyl radical is similar to that of the o-pyridyl radical reported in the early study.
基金supported by the US National Science Foundation(No.CHE-1566636)
文摘The ultraviolet (UV) photodissociation of jet-cooled 1-pentyl radical is investigated in the wavelength region of 236-254 nm using the high-n Rydberg-atom time-of-flight (HRTOF) technique. The H-atom photofragment yield spectrum of the 1-pentyl radical shows a broad UV absorption feature peaking near 245 nm, similar to the 2pz→3s absorption bands of ethyl and n-propyl. The center-of-mass translational energy distribution, P(ET), of the H+CsH10 product channel is bimodal, with a slow peak at -5 kcal/mol and a fast peak at -50 kcal/mol. The fraction of the average translational energy release in the total available energy, (fT), is 0.30, with those of the slow and fast components being 0.13 and 0.58, respectively. The slow component has an isotropic product angular distribution, while the fast component is anisotropic with an anisotropy parameter -0.4. The bimodal translational energy and angular distributions of the H+C5H10 products indicate two H-atom elimination channels in the photodissociation of 1-pentyl: (i) a direct, prompt dissociation from the electronic excited state and/or the repulsive part of the ground electronic state potential energy surface; and (ii) a unimolecular dissociation of internally hot radical in the ground electronic state after internal conversion from the electronic excited state.
基金supported by the US National Science Foundation (grant number CHE-1566636)UC MEXUS-CONACYT Collaborative Grant (CN-1668)DGAPA-UNAM for support through Project PAPIIT IN-115916.
文摘Two-photon dissociation dynamics of the OH radical is studied using the high-n Rydberg atom time-of-flight(HRTOF) technique. The H(2 S)+O(1 D) and H(2 S)+O(1 S) product channels are observed in the dissociation of the OH radical on the 22Π and B2Σ+repulsive states, respectively, from sequential two-photon excitation via the A2Σ+(v′=2, J′=0.5-2.5)state. Both H+O product channels have anisotropic angular distributions, with β=-0.97 for H(2 S)+O(1 D) and 1.97 for H(2 S)+O(1 S). The anisotropic angular distributions are consistent with a mechanism of OH direct dissociation on the repulsive potential energy curves(PECs) leading to the H+O products. The OH bond dissociation energy D0(O-H) is determined to be 35580±15 cm-1.