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Thom H Dunning - One of the best experts on this subject based on the ideXlab platform.
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bonding in sulfur oxygen compounds hso soh and soo OSO an example of recoupled pair π bonding
Journal of Chemical Theory and Computation, 2013Co-Authors: Beth A Lindquist, Tyler Y Takeshita, David E Woon, Thom H DunningAbstract:The ground states (X2A″) of HSO and SOH are extremely close in energy, yet their molecular structures differ dramatically, e.g., re(SO) is 1.485 A in HSO and 1.632 A in SOH. The SO bond is also much stronger in HSO than in SOH: 100.3 kcal/mol versus 78.8 kcal/mol [RCCSD(T)-F12/AVTZ]. Similar differences are found in the SO2 isomers, SOO and OSO, depending on whether the second oxygen atom binds to oxygen or sulfur. We report generalized valence bond and RCCSD(T)-F12 calculations on HSO/SOH and OSO/SOO and analyze the bonding in all four species. We find that HSO has a shorter and stronger SO bond than SOH due to the presence of a recoupled pair bond in the π(a″) system of HSO. Similarly, the bonding in SOO and OSO differs greatly. SOO is like ozone and has substantial diradical character, while OSO has two recoupled pair π bonds and negligible diradical character. The ability of the sulfur atom to form recoupled pair bonds provides a natural explanation for the dramatic variation in the bonding in these a...
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Bonding in Sulfur-Oxygen Compounds-HSO/SOH and SOO/OSO: An Example of Recoupled Pair π Bonding.
Journal of Chemical Theory and Computation, 2013Co-Authors: Beth A Lindquist, Tyler Y Takeshita, David E Woon, Thom H DunningAbstract:The ground states (X2A″) of HSO and SOH are extremely close in energy, yet their molecular structures differ dramatically, e.g., re(SO) is 1.485 A in HSO and 1.632 A in SOH. The SO bond is also much stronger in HSO than in SOH: 100.3 kcal/mol versus 78.8 kcal/mol [RCCSD(T)-F12/AVTZ]. Similar differences are found in the SO2 isomers, SOO and OSO, depending on whether the second oxygen atom binds to oxygen or sulfur. We report generalized valence bond and RCCSD(T)-F12 calculations on HSO/SOH and OSO/SOO and analyze the bonding in all four species. We find that HSO has a shorter and stronger SO bond than SOH due to the presence of a recoupled pair bond in the π(a″) system of HSO. Similarly, the bonding in SOO and OSO differs greatly. SOO is like ozone and has substantial diradical character, while OSO has two recoupled pair π bonds and negligible diradical character. The ability of the sulfur atom to form recoupled pair bonds provides a natural explanation for the dramatic variation in the bonding in these a...
Beth A Lindquist - One of the best experts on this subject based on the ideXlab platform.
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bonding in sulfur oxygen compounds hso soh and soo OSO an example of recoupled pair π bonding
Journal of Chemical Theory and Computation, 2013Co-Authors: Beth A Lindquist, Tyler Y Takeshita, David E Woon, Thom H DunningAbstract:The ground states (X2A″) of HSO and SOH are extremely close in energy, yet their molecular structures differ dramatically, e.g., re(SO) is 1.485 A in HSO and 1.632 A in SOH. The SO bond is also much stronger in HSO than in SOH: 100.3 kcal/mol versus 78.8 kcal/mol [RCCSD(T)-F12/AVTZ]. Similar differences are found in the SO2 isomers, SOO and OSO, depending on whether the second oxygen atom binds to oxygen or sulfur. We report generalized valence bond and RCCSD(T)-F12 calculations on HSO/SOH and OSO/SOO and analyze the bonding in all four species. We find that HSO has a shorter and stronger SO bond than SOH due to the presence of a recoupled pair bond in the π(a″) system of HSO. Similarly, the bonding in SOO and OSO differs greatly. SOO is like ozone and has substantial diradical character, while OSO has two recoupled pair π bonds and negligible diradical character. The ability of the sulfur atom to form recoupled pair bonds provides a natural explanation for the dramatic variation in the bonding in these a...
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Bonding in Sulfur-Oxygen Compounds-HSO/SOH and SOO/OSO: An Example of Recoupled Pair π Bonding.
Journal of Chemical Theory and Computation, 2013Co-Authors: Beth A Lindquist, Tyler Y Takeshita, David E Woon, Thom H DunningAbstract:The ground states (X2A″) of HSO and SOH are extremely close in energy, yet their molecular structures differ dramatically, e.g., re(SO) is 1.485 A in HSO and 1.632 A in SOH. The SO bond is also much stronger in HSO than in SOH: 100.3 kcal/mol versus 78.8 kcal/mol [RCCSD(T)-F12/AVTZ]. Similar differences are found in the SO2 isomers, SOO and OSO, depending on whether the second oxygen atom binds to oxygen or sulfur. We report generalized valence bond and RCCSD(T)-F12 calculations on HSO/SOH and OSO/SOO and analyze the bonding in all four species. We find that HSO has a shorter and stronger SO bond than SOH due to the presence of a recoupled pair bond in the π(a″) system of HSO. Similarly, the bonding in SOO and OSO differs greatly. SOO is like ozone and has substantial diradical character, while OSO has two recoupled pair π bonds and negligible diradical character. The ability of the sulfur atom to form recoupled pair bonds provides a natural explanation for the dramatic variation in the bonding in these a...
B. Funke - One of the best experts on this subject based on the ideXlab platform.
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six years of mesospheric co estimated from ground based frequency switched microwave radiometry at 57 n compared with satellite instruments
Atmospheric Measurement Techniques, 2012Co-Authors: Peter Forkman, O. M. Christensen, P. Eriksson, J. Urban, B. FunkeAbstract:Abstract. Measurements of mesospheric carbon monoxide, CO, provide important information about the dynamics in the mesosphere region since CO has a long lifetime at these altitudes. Ground-based measurements of mesospheric CO made at the Onsala Space Observatory, OSO, (57° N, 12° E) are presented. The dataset covers the period 2002–2008 and is hence uniquely long for ground-based observations. The simple and stable 115 GHz frequency-switched radiometer, calibration method, retrieval procedure and error characterization are described. A comparison between our measurements and co-located CO measurements from the satellite sensors ACE-FTS on Scisat (v2.2), MLS on Aura (v3-3), MIPAS on Envisat (V3O_CO_12 + 13 and V4O_CO_200) and SMR on Odin (v225 and v021) is carried out. Our instrument, OSO, and the four satellite instruments show the same general variation of the vertical distribution of mesospheric CO in both the annual cycle and in shorter time period events, with high CO mixing ratios during winter and very low amounts during summer in the observed 55–100 km altitude range. During 2004–2008 the agreement of the OSO instrument and the satellite sensors ACE-FTS, MLS and MIPAS (200) is good in the altitude range 55–70 km. Above 70 km, OSO shows up to 25% higher CO column values compared to both ACE and MLS. For the time period 2002–2004, CO from MIPAS (12 + 13) is up to 50% lower than OSO between 55 and 70 km. Mesospheric CO from the two versions of SMR deviates up to ±65% when compared to OSO, but the analysis is based on only a few co-locations.
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Six years of mesospheric CO estimated from ground-based frequency-switched microwave radiometry at 57° N compared with satellite instruments
Atmospheric Measurement Techniques, 2012Co-Authors: Peter Forkman, O. M. Christensen, P. Eriksson, J. Urban, B. FunkeAbstract:Abstract. Measurements of mesospheric carbon monoxide, CO, provide important information about the dynamics in the mesosphere region since CO has a long lifetime at these altitudes. Ground-based measurements of mesospheric CO made at the Onsala Space Observatory, OSO, (57° N, 12° E) are presented. The dataset covers the period 2002–2008 and is hence uniquely long for ground-based observations. The simple and stable 115 GHz frequency-switched radiometer, calibration method, retrieval procedure and error characterization are described. A comparison between our measurements and co-located CO measurements from the satellite sensors ACE-FTS on Scisat (v2.2), MLS on Aura (v3-3), MIPAS on Envisat (V3O_CO_12 + 13 and V4O_CO_200) and SMR on Odin (v225 and v021) is carried out. Our instrument, OSO, and the four satellite instruments show the same general variation of the vertical distribution of mesospheric CO in both the annual cycle and in shorter time period events, with high CO mixing ratios during winter and very low amounts during summer in the observed 55–100 km altitude range. During 2004–2008 the agreement of the OSO instrument and the satellite sensors ACE-FTS, MLS and MIPAS (200) is good in the altitude range 55–70 km. Above 70 km, OSO shows up to 25% higher CO column values compared to both ACE and MLS. For the time period 2002–2004, CO from MIPAS (12 + 13) is up to 50% lower than OSO between 55 and 70 km. Mesospheric CO from the two versions of SMR deviates up to ±65% when compared to OSO, but the analysis is based on only a few co-locations.
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Six years of mesospheric CO estimated from ground-based frequency-switched microwave radiometry at 57° N compared with satellite instruments
Atmospheric Measurement Techniques Discussions, 2012Co-Authors: Peter Forkman, O. M. Christensen, P. Eriksson, J. Urban, B. FunkeAbstract:Abstract. Measurements of mesospheric carbon monoxide, CO, provide important information about the dynamics in the mesosphere region since CO has a long lifetime at these altitudes. Ground-based measurements of mesospheric CO made at the Onsala Space Observatory, OSO, (57° N, 12° E) are presented. The dataset covers the period 2002–2008 and is hence uniquely long. The simple and stable 115 GHz frequency-switched radiometer, calibration method, retrieval procedure and error characterization are described. A comparison between our measurements and co-located CO measurements from the satellite sensors ACE-FTS on Scisat (v2.2), MLS on Aura (v3-3), MIPAS on Envisat (V3O_CO_12 + 13 and V4O_CO_200) and SMR on Odin (v225 and v021) is done. Our instrument, OSO, and the four satellite instruments show the same general variation of the vertical distribution of mesospheric CO in both the annual cycle and in shorter time period events with high CO mixing ratios during winter and very low amounts during summer in the observed 55–85 km altitude range. During 2004–2008 the agreement of the OSO instrument and the satellite sensors ACE-FTS, MLS and MIPAS(200) is good in the altitude range 55–70 km. Above 70 km OSO show up to 25% higher CO column values compared to both ACE and MLS. For the time period 2002–2003 CO from MIPAS(12 + 13) is up to 60% lower than OSO between 55 and 70 km. Mesospheric CO from the two versions of SMR deviates up to ±65% when compared to OSO, but the analysis is based on only a few co-locations.
Gary J Schrobilgen - One of the best experts on this subject based on the ideXlab platform.
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the OSO 3 f and mu f OSO 3 f 2 cations their syntheses and study by raman and 19 f nmr spectroscopy and electron structure calculations and x ray crystal structures of OSO 3 f pnf 6 pn as sb OSO 3 f hf 2 asf 6 OSO 3 f hf sbf 6 and OSO 3 f sb 3 f 16
Inorganic Chemistry, 2002Co-Authors: Michael Gerken, David A Dixon, Gary J SchrobilgenAbstract:: The fluoride ion donor properties of OSO(3)F(2) have been investigated. The salts [OSO(3)F][AsF(6)], [OSO(3)F][HF](2)[AsF(6)], mu-F(OSO(3)F)(2)[AsF(6)], [OSO(3)F][HF](2)[SbF(6)], and [OSO(3)F][HF][SbF(6)] have been prepared by reaction of OSO(3)F(2) with AsF(5) and SbF(5) in HF solvent and have been characterized in the solid state by Raman spectroscopy. The single-crystal X-ray diffraction studies of [OSO(3)F][AsF(6)] (P2(1)/n, a = 7.0001(11) A, c = 8.8629(13) A, beta = 92.270(7) degrees, Z = 4, and R(1) = 0.0401 at -126 degrees C), [OSO(3)F][SbF(6)] (P2(1)/c, a = 5.4772(14) A, b = 10.115(3) A, c = 12.234(3) A, beta = 99.321(5) degrees, Z = 4, and R(1) = 0.0325 at -173 degrees C), [OSO(3)F][HF](2)[AsF(6)] (P2(1)/n, a = 5.1491(9) A, b = 8.129(2) A, c = 19.636(7) A, beta = 95.099(7) degrees, Z = 4, and R(1) = 0.0348 at -117 degrees C), and [OSO(3)F][HF][SbF(6)] (Pc, a = 5.244(4) A, b = 9.646(6) A, c = 15.269(10) A, beta = 97.154(13) degrees, Z = 4, and R(1) = 0.0558 at -133 degrees C) have shown that the OSO(3)F(+) cations exhibit strong contacts to the anions and HF solvent molecules giving rise to cyclic, dimeric structures in which the osmium atoms have coordination numbers of 6. The reaction of OSO(3)F(2) with neat SbF(5) yielded [OSO(3)F][Sb(3)F(16)], which has been characterized by (19)F NMR spectroscopy in SbF(5) and SO(2)ClF solvents and by Raman spectroscopy and single-crystal X-ray diffraction in the solid state (P4(1)m, a = 10.076(6) A, c = 7.585(8) A, Z = 2, and R(1) = 0.0858 at -113 degrees C). The weak fluoride ion basicity of the Sb(3)F(16)(-) anion resulted in an OSO(3)F(+) cation (C(3)(v) point symmetry) that is well isolated from the anion and in which the osmium is four-coordinate. The geometrical parameters and vibrational frequencies of OSO(3)F(+), ReO(3)F, mu-F(OSO(3)F)(2)(+), (FO(3)Os--FPnF(5))(2), and (FO(3)Os--(HF)(2)--FPnF(5))(2) (Pn = As, Sb) have been calculated using density functional theory methods.
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The OSO(3)F(+) and mu-F(OSO(3)F)(2)(+) cations: their syntheses and study by Raman and (19)F NMR spectroscopy and electron structure calculations and X-ray crystal structures of [OSO(3)F][PnF(6)] (Pn = As, Sb), [OSO(3)F][HF](2)[AsF(6)], [OSO(3)F][HF]
Inorganic Chemistry, 2002Co-Authors: Michael Gerken, David A Dixon, Gary J SchrobilgenAbstract:: The fluoride ion donor properties of OSO(3)F(2) have been investigated. The salts [OSO(3)F][AsF(6)], [OSO(3)F][HF](2)[AsF(6)], mu-F(OSO(3)F)(2)[AsF(6)], [OSO(3)F][HF](2)[SbF(6)], and [OSO(3)F][HF][SbF(6)] have been prepared by reaction of OSO(3)F(2) with AsF(5) and SbF(5) in HF solvent and have been characterized in the solid state by Raman spectroscopy. The single-crystal X-ray diffraction studies of [OSO(3)F][AsF(6)] (P2(1)/n, a = 7.0001(11) A, c = 8.8629(13) A, beta = 92.270(7) degrees, Z = 4, and R(1) = 0.0401 at -126 degrees C), [OSO(3)F][SbF(6)] (P2(1)/c, a = 5.4772(14) A, b = 10.115(3) A, c = 12.234(3) A, beta = 99.321(5) degrees, Z = 4, and R(1) = 0.0325 at -173 degrees C), [OSO(3)F][HF](2)[AsF(6)] (P2(1)/n, a = 5.1491(9) A, b = 8.129(2) A, c = 19.636(7) A, beta = 95.099(7) degrees, Z = 4, and R(1) = 0.0348 at -117 degrees C), and [OSO(3)F][HF][SbF(6)] (Pc, a = 5.244(4) A, b = 9.646(6) A, c = 15.269(10) A, beta = 97.154(13) degrees, Z = 4, and R(1) = 0.0558 at -133 degrees C) have shown that the OSO(3)F(+) cations exhibit strong contacts to the anions and HF solvent molecules giving rise to cyclic, dimeric structures in which the osmium atoms have coordination numbers of 6. The reaction of OSO(3)F(2) with neat SbF(5) yielded [OSO(3)F][Sb(3)F(16)], which has been characterized by (19)F NMR spectroscopy in SbF(5) and SO(2)ClF solvents and by Raman spectroscopy and single-crystal X-ray diffraction in the solid state (P4(1)m, a = 10.076(6) A, c = 7.585(8) A, Z = 2, and R(1) = 0.0858 at -113 degrees C). The weak fluoride ion basicity of the Sb(3)F(16)(-) anion resulted in an OSO(3)F(+) cation (C(3)(v) point symmetry) that is well isolated from the anion and in which the osmium is four-coordinate. The geometrical parameters and vibrational frequencies of OSO(3)F(+), ReO(3)F, mu-F(OSO(3)F)(2)(+), (FO(3)Os--FPnF(5))(2), and (FO(3)Os--(HF)(2)--FPnF(5))(2) (Pn = As, Sb) have been calculated using density functional theory methods.
Tyler Y Takeshita - One of the best experts on this subject based on the ideXlab platform.
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bonding in sulfur oxygen compounds hso soh and soo OSO an example of recoupled pair π bonding
Journal of Chemical Theory and Computation, 2013Co-Authors: Beth A Lindquist, Tyler Y Takeshita, David E Woon, Thom H DunningAbstract:The ground states (X2A″) of HSO and SOH are extremely close in energy, yet their molecular structures differ dramatically, e.g., re(SO) is 1.485 A in HSO and 1.632 A in SOH. The SO bond is also much stronger in HSO than in SOH: 100.3 kcal/mol versus 78.8 kcal/mol [RCCSD(T)-F12/AVTZ]. Similar differences are found in the SO2 isomers, SOO and OSO, depending on whether the second oxygen atom binds to oxygen or sulfur. We report generalized valence bond and RCCSD(T)-F12 calculations on HSO/SOH and OSO/SOO and analyze the bonding in all four species. We find that HSO has a shorter and stronger SO bond than SOH due to the presence of a recoupled pair bond in the π(a″) system of HSO. Similarly, the bonding in SOO and OSO differs greatly. SOO is like ozone and has substantial diradical character, while OSO has two recoupled pair π bonds and negligible diradical character. The ability of the sulfur atom to form recoupled pair bonds provides a natural explanation for the dramatic variation in the bonding in these a...
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Bonding in Sulfur-Oxygen Compounds-HSO/SOH and SOO/OSO: An Example of Recoupled Pair π Bonding.
Journal of Chemical Theory and Computation, 2013Co-Authors: Beth A Lindquist, Tyler Y Takeshita, David E Woon, Thom H DunningAbstract:The ground states (X2A″) of HSO and SOH are extremely close in energy, yet their molecular structures differ dramatically, e.g., re(SO) is 1.485 A in HSO and 1.632 A in SOH. The SO bond is also much stronger in HSO than in SOH: 100.3 kcal/mol versus 78.8 kcal/mol [RCCSD(T)-F12/AVTZ]. Similar differences are found in the SO2 isomers, SOO and OSO, depending on whether the second oxygen atom binds to oxygen or sulfur. We report generalized valence bond and RCCSD(T)-F12 calculations on HSO/SOH and OSO/SOO and analyze the bonding in all four species. We find that HSO has a shorter and stronger SO bond than SOH due to the presence of a recoupled pair bond in the π(a″) system of HSO. Similarly, the bonding in SOO and OSO differs greatly. SOO is like ozone and has substantial diradical character, while OSO has two recoupled pair π bonds and negligible diradical character. The ability of the sulfur atom to form recoupled pair bonds provides a natural explanation for the dramatic variation in the bonding in these a...
