A Critical Evaluation of Vibrational Stark Effect (VSE) Probes with the Local Vibrational Mode Theory
Over the past two decades, the vibrational Stark effect has become an important tool to measure and analyze the in situ electric field strength in various chemical environments with infrared spectroscopy. The underlying assumption of this effect is that the normal stretching mode of a target bond su...
| Main Authors: | , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2020-04-01
|
| Series: | Sensors |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1424-8220/20/8/2358 |
| _version_ | 1797570046665424896 |
|---|---|
| author | Niraj Verma Yunwen Tao Wenli Zou Xia Chen Xin Chen Marek Freindorf Elfi Kraka |
| author_facet | Niraj Verma Yunwen Tao Wenli Zou Xia Chen Xin Chen Marek Freindorf Elfi Kraka |
| author_sort | Niraj Verma |
| collection | DOAJ |
| description | Over the past two decades, the vibrational Stark effect has become an important tool to measure and analyze the in situ electric field strength in various chemical environments with infrared spectroscopy. The underlying assumption of this effect is that the normal stretching mode of a target bond such as CO or CN of a reporter molecule (termed vibrational Stark effect probe) is localized and free from mass-coupling from other internal coordinates, so that its frequency shift directly reflects the influence of the vicinal electric field. However, the validity of this essential assumption has never been assessed. Given the fact that normal modes are generally delocalized because of mass-coupling, this analysis was overdue. Therefore, we carried out a comprehensive evaluation of 68 vibrational Stark effect probes and candidates to quantify the degree to which their target normal vibration of probe bond stretching is decoupled from local vibrations driven by other internal coordinates. The unique tool we used is the local mode analysis originally introduced by Konkoli and Cremer, in particular the decomposition of normal modes into local mode contributions. Based on our results, we recommend 31 polyatomic molecules with localized target bonds as ideal vibrational Stark effect probe candidates. |
| first_indexed | 2024-03-10T20:19:31Z |
| format | Article |
| id | doaj.art-aaff4173ad2d4995b6b729951bdfd1f6 |
| institution | Directory Open Access Journal |
| issn | 1424-8220 |
| language | English |
| last_indexed | 2024-03-10T20:19:31Z |
| publishDate | 2020-04-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Sensors |
| spelling | doaj.art-aaff4173ad2d4995b6b729951bdfd1f62023-11-19T22:16:37ZengMDPI AGSensors1424-82202020-04-01208235810.3390/s20082358A Critical Evaluation of Vibrational Stark Effect (VSE) Probes with the Local Vibrational Mode TheoryNiraj Verma0Yunwen Tao1Wenli Zou2Xia Chen3Xin Chen4Marek Freindorf5Elfi Kraka6Department of Chemistry, Southern Methodist University, 3215 Daniel Avenue, Dallas, TX 75275-0314, USADepartment of Chemistry, Southern Methodist University, 3215 Daniel Avenue, Dallas, TX 75275-0314, USAInstitute of Modern Physics, Northwest University, Xi’an 710127, ChinaHubei Key Laboratory of Natural Medicinal Chemistry and Resource Evaluation, School of Pharmacy, Tongji Medical College, Huazhong University of Science and Technology, Wuhan 430030, ChinaLaboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, ChinaDepartment of Chemistry, Southern Methodist University, 3215 Daniel Avenue, Dallas, TX 75275-0314, USADepartment of Chemistry, Southern Methodist University, 3215 Daniel Avenue, Dallas, TX 75275-0314, USAOver the past two decades, the vibrational Stark effect has become an important tool to measure and analyze the in situ electric field strength in various chemical environments with infrared spectroscopy. The underlying assumption of this effect is that the normal stretching mode of a target bond such as CO or CN of a reporter molecule (termed vibrational Stark effect probe) is localized and free from mass-coupling from other internal coordinates, so that its frequency shift directly reflects the influence of the vicinal electric field. However, the validity of this essential assumption has never been assessed. Given the fact that normal modes are generally delocalized because of mass-coupling, this analysis was overdue. Therefore, we carried out a comprehensive evaluation of 68 vibrational Stark effect probes and candidates to quantify the degree to which their target normal vibration of probe bond stretching is decoupled from local vibrations driven by other internal coordinates. The unique tool we used is the local mode analysis originally introduced by Konkoli and Cremer, in particular the decomposition of normal modes into local mode contributions. Based on our results, we recommend 31 polyatomic molecules with localized target bonds as ideal vibrational Stark effect probe candidates.https://www.mdpi.com/1424-8220/20/8/2358Stark spectroscopyvibrational Stark effectVSElocal vibrational mode theorynormal mode decompositionvibrational Stark effect probes |
| spellingShingle | Niraj Verma Yunwen Tao Wenli Zou Xia Chen Xin Chen Marek Freindorf Elfi Kraka A Critical Evaluation of Vibrational Stark Effect (VSE) Probes with the Local Vibrational Mode Theory Sensors Stark spectroscopy vibrational Stark effect VSE local vibrational mode theory normal mode decomposition vibrational Stark effect probes |
| title | A Critical Evaluation of Vibrational Stark Effect (VSE) Probes with the Local Vibrational Mode Theory |
| title_full | A Critical Evaluation of Vibrational Stark Effect (VSE) Probes with the Local Vibrational Mode Theory |
| title_fullStr | A Critical Evaluation of Vibrational Stark Effect (VSE) Probes with the Local Vibrational Mode Theory |
| title_full_unstemmed | A Critical Evaluation of Vibrational Stark Effect (VSE) Probes with the Local Vibrational Mode Theory |
| title_short | A Critical Evaluation of Vibrational Stark Effect (VSE) Probes with the Local Vibrational Mode Theory |
| title_sort | critical evaluation of vibrational stark effect vse probes with the local vibrational mode theory |
| topic | Stark spectroscopy vibrational Stark effect VSE local vibrational mode theory normal mode decomposition vibrational Stark effect probes |
| url | https://www.mdpi.com/1424-8220/20/8/2358 |
| work_keys_str_mv | AT nirajverma acriticalevaluationofvibrationalstarkeffectvseprobeswiththelocalvibrationalmodetheory AT yunwentao acriticalevaluationofvibrationalstarkeffectvseprobeswiththelocalvibrationalmodetheory AT wenlizou acriticalevaluationofvibrationalstarkeffectvseprobeswiththelocalvibrationalmodetheory AT xiachen acriticalevaluationofvibrationalstarkeffectvseprobeswiththelocalvibrationalmodetheory AT xinchen acriticalevaluationofvibrationalstarkeffectvseprobeswiththelocalvibrationalmodetheory AT marekfreindorf acriticalevaluationofvibrationalstarkeffectvseprobeswiththelocalvibrationalmodetheory AT elfikraka acriticalevaluationofvibrationalstarkeffectvseprobeswiththelocalvibrationalmodetheory AT nirajverma criticalevaluationofvibrationalstarkeffectvseprobeswiththelocalvibrationalmodetheory AT yunwentao criticalevaluationofvibrationalstarkeffectvseprobeswiththelocalvibrationalmodetheory AT wenlizou criticalevaluationofvibrationalstarkeffectvseprobeswiththelocalvibrationalmodetheory AT xiachen criticalevaluationofvibrationalstarkeffectvseprobeswiththelocalvibrationalmodetheory AT xinchen criticalevaluationofvibrationalstarkeffectvseprobeswiththelocalvibrationalmodetheory AT marekfreindorf criticalevaluationofvibrationalstarkeffectvseprobeswiththelocalvibrationalmodetheory AT elfikraka criticalevaluationofvibrationalstarkeffectvseprobeswiththelocalvibrationalmodetheory |