Inefficient intramolecular vibrational energy redistribution for the H + HO2 reaction and negative internal energy dependence for its rate constant
Quasiclassical trajectories (QCT) and newly constructed global potential energy surfaces are used to compute thermal and nonthermal rate constants for the H + HO2 reaction. The thermal QCTs rate constants are up to 50% smaller than transition state theory (TST) rate constants based on the same level...
| Main Authors: | , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Frontiers Media S.A.
2022-10-01
|
| Series: | Frontiers in Physics |
| Subjects: | |
| Online Access: | https://www.frontiersin.org/articles/10.3389/fphy.2022.1003010/full |
| _version_ | 1828107044583899136 |
|---|---|
| author | Ahren W. Jasper Daniel R. Moberg Yujie Tao Stephen J. Klippenstein Raghu Sivaramakrishnan |
| author_facet | Ahren W. Jasper Daniel R. Moberg Yujie Tao Stephen J. Klippenstein Raghu Sivaramakrishnan |
| author_sort | Ahren W. Jasper |
| collection | DOAJ |
| description | Quasiclassical trajectories (QCT) and newly constructed global potential energy surfaces are used to compute thermal and nonthermal rate constants for the H + HO2 reaction. The thermal QCTs rate constants are up to 50% smaller than transition state theory (TST) rate constants based on the same level of electronic structure theory. This reduction is demonstrated to result from inefficient intramolecular vibrational energy redistribution (IVR) in the transient H2O2 well, with a significant fraction of trajectories that reach the H2O2 well promptly dissociating back to reactants instead of via the heavily statistically favored 2OH channel. The nonstatistical reduction factor, κIVR, that quantifies this effect is shown to increase in importance with temperature, with κIVR = 0.81 at 300 K and 0.47 at 2500 K. Finally, we show that inefficient IVR causes H + HO2 rate constants mediated by H2O2 to depend inversely on the initial vibrational excitation of HO2. |
| first_indexed | 2024-04-11T10:26:48Z |
| format | Article |
| id | doaj.art-317020ce94524cab86f742097a585a58 |
| institution | Directory Open Access Journal |
| issn | 2296-424X |
| language | English |
| last_indexed | 2024-04-11T10:26:48Z |
| publishDate | 2022-10-01 |
| publisher | Frontiers Media S.A. |
| record_format | Article |
| series | Frontiers in Physics |
| spelling | doaj.art-317020ce94524cab86f742097a585a582022-12-22T04:29:34ZengFrontiers Media S.A.Frontiers in Physics2296-424X2022-10-011010.3389/fphy.2022.10030101003010Inefficient intramolecular vibrational energy redistribution for the H + HO2 reaction and negative internal energy dependence for its rate constantAhren W. JasperDaniel R. MobergYujie TaoStephen J. KlippensteinRaghu SivaramakrishnanQuasiclassical trajectories (QCT) and newly constructed global potential energy surfaces are used to compute thermal and nonthermal rate constants for the H + HO2 reaction. The thermal QCTs rate constants are up to 50% smaller than transition state theory (TST) rate constants based on the same level of electronic structure theory. This reduction is demonstrated to result from inefficient intramolecular vibrational energy redistribution (IVR) in the transient H2O2 well, with a significant fraction of trajectories that reach the H2O2 well promptly dissociating back to reactants instead of via the heavily statistically favored 2OH channel. The nonstatistical reduction factor, κIVR, that quantifies this effect is shown to increase in importance with temperature, with κIVR = 0.81 at 300 K and 0.47 at 2500 K. Finally, we show that inefficient IVR causes H + HO2 rate constants mediated by H2O2 to depend inversely on the initial vibrational excitation of HO2.https://www.frontiersin.org/articles/10.3389/fphy.2022.1003010/fulltransition state theory (TST)intramolecular vibrational energy redistribution (IVR)quasiclassical trajectory (QCT)nonthermal kineticsH2/O2 |
| spellingShingle | Ahren W. Jasper Daniel R. Moberg Yujie Tao Stephen J. Klippenstein Raghu Sivaramakrishnan Inefficient intramolecular vibrational energy redistribution for the H + HO2 reaction and negative internal energy dependence for its rate constant Frontiers in Physics transition state theory (TST) intramolecular vibrational energy redistribution (IVR) quasiclassical trajectory (QCT) nonthermal kinetics H2/O2 |
| title | Inefficient intramolecular vibrational energy redistribution for the H + HO2 reaction and negative internal energy dependence for its rate constant |
| title_full | Inefficient intramolecular vibrational energy redistribution for the H + HO2 reaction and negative internal energy dependence for its rate constant |
| title_fullStr | Inefficient intramolecular vibrational energy redistribution for the H + HO2 reaction and negative internal energy dependence for its rate constant |
| title_full_unstemmed | Inefficient intramolecular vibrational energy redistribution for the H + HO2 reaction and negative internal energy dependence for its rate constant |
| title_short | Inefficient intramolecular vibrational energy redistribution for the H + HO2 reaction and negative internal energy dependence for its rate constant |
| title_sort | inefficient intramolecular vibrational energy redistribution for the h ho2 reaction and negative internal energy dependence for its rate constant |
| topic | transition state theory (TST) intramolecular vibrational energy redistribution (IVR) quasiclassical trajectory (QCT) nonthermal kinetics H2/O2 |
| url | https://www.frontiersin.org/articles/10.3389/fphy.2022.1003010/full |
| work_keys_str_mv | AT ahrenwjasper inefficientintramolecularvibrationalenergyredistributionforthehho2reactionandnegativeinternalenergydependenceforitsrateconstant AT danielrmoberg inefficientintramolecularvibrationalenergyredistributionforthehho2reactionandnegativeinternalenergydependenceforitsrateconstant AT yujietao inefficientintramolecularvibrationalenergyredistributionforthehho2reactionandnegativeinternalenergydependenceforitsrateconstant AT stephenjklippenstein inefficientintramolecularvibrationalenergyredistributionforthehho2reactionandnegativeinternalenergydependenceforitsrateconstant AT raghusivaramakrishnan inefficientintramolecularvibrationalenergyredistributionforthehho2reactionandnegativeinternalenergydependenceforitsrateconstant |