{"doi":"10.1063/1.1739391","title":"The vibrational Stokes shift of water (HOD in D2O)","abstract":"<jats:p>The vibrational Stokes shift of the OH stretching transition νOH of water is the shift between the ground-state absorption and the excited-state (v=1) emission. A recent measurement on HOD in D2O solvent [S. Woutersen and H. J. Bakker, Phys. Rev. Lett. 83, 2077 (1999)] of a 70 cm−1 redshift, and a subsequent calculation of a 57 cm−1 redshift using equilibrium molecular dynamics simulations [C. P. Lawrence and J. L. Skinner, J. Chem. Phys. 117, 8847 (2002)] were in good agreement. We now report extensive measurements of the vibrational Stokes shift in HOD/D2O using an ultrafast IR pump, Raman probe method. The vibrational Stokes shift is seen to depend on the pump pulse frequency and on time delay; by varying these parameters it can be made to range from 112 to −32 cm−1 (negative values indicate a blueshift in the excited state). The equilibrium vibrational Stokes shift is actually a negative rather than a positive quantity. Possible reasons for the disagreement between experiment and theory are briefly discussed.</jats:p>","journal":"The Journal of Chemical Physics","year":2004,"id":671905,"datarank":0.5050943744979712,"base_score":3.367295829986474,"endowment":3.367295829986474,"self_citation_contribution":0.5050943744979712,"citation_network_contribution":0.0,"self_endowment_contribution":0.5050943744979712,"citer_contribution":0.0,"corpus_percentile":null,"corpus_rank":null,"citation_count":28,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":null,"is_data_producer":false,"deposit_databanks":null,"is_oa":false,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":null,"fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":1755412,"name":"Yoonsoo Pang","orcid":null,"position":1,"is_corresponding":false},{"id":1755413,"name":"Dana D. Dlott","orcid":null,"position":2,"is_corresponding":false},{"id":285063,"name":"Zhaohui Wang","orcid":"0000-0001-7994-7464","position":0,"is_corresponding":false}],"reference_count":0,"raw_metadata":{"has_enrichment":true,"resolved":true,"title":"The vibrational Stokes shift of water (HOD in D2O)","abstract":"<jats:p>The vibrational Stokes shift of the OH stretching transition νOH of water is the shift between the ground-state absorption and the excited-state (v=1) emission. A recent measurement on HOD in D2O solvent [S. Woutersen and H. J. Bakker, Phys. Rev. Lett. 83, 2077 (1999)] of a 70 cm−1 redshift, and a subsequent calculation of a 57 cm−1 redshift using equilibrium molecular dynamics simulations [C. P. Lawrence and J. L. Skinner, J. Chem. Phys. 117, 8847 (2002)] were in good agreement. We now report extensive measurements of the vibrational Stokes shift in HOD/D2O using an ultrafast IR pump, Raman probe method. The vibrational Stokes shift is seen to depend on the pump pulse frequency and on time delay; by varying these parameters it can be made to range from 112 to −32 cm−1 (negative values indicate a blueshift in the excited state). The equilibrium vibrational Stokes shift is actually a negative rather than a positive quantity. Possible reasons for the disagreement between experiment and theory are briefly discussed.</jats:p>","is_dataset_classified":null,"base_score":3.367295829986474,"endowment":3.367295829986474,"datacite_reuse_total":0,"file_count":0,"downloads":0,"views":0,"has_version_chain":false,"is_dataset":false,"is_oa":false,"pmid":"15267756","pmcid":null,"openalex_id":"https://openalex.org/W1561855526","authors":[],"funders":[],"total_grants":0,"fwci":3.2665,"citation_percentile":0.92006152,"influential_citations":0,"citation_trend":[{"year":2012,"count":1},{"year":2014,"count":1},{"year":2015,"count":1},{"year":2016,"count":1},{"year":2020,"count":1},{"year":2021,"count":1},{"year":2022,"count":1},{"year":2025,"count":1}],"oa_status":"closed","license":null,"oa_locations":[{"url":"https://pubs.aip.org/aip/jcp/article-pdf/120/18/8345/19031264/8345_1_online.pdf","host_type":"publisher"},{"url":"https://doi.org/10.1063/1.1739391","host_type":"journal"},{"url":"https://pubmed.ncbi.nlm.nih.gov/15267756","host_type":"repository"}],"fields_of_study":["Spectroscopy and Quantum Chemical Studies","Atmospheric Ozone and Climate","Spectroscopy and Laser Applications"],"mesh_terms":[],"keywords":["Stokes shift","Blueshift","Excited state","Redshift","Atomic physics","Raman spectroscopy","Ground state","Chemistry","Ultrashort pulse","Absorption (acoustics)","Physics","Laser","Optics","Quantum mechanics","Luminescence"],"sdg_mappings":[{"sdg_number":0,"sdg_label":"Clean water and sanitation"}],"linked_datasets":[],"clinical_trials":[],"software_tools":[],"database_accessions":[],"source":"live","citation_network_status":"fetched"},"created_at":"2026-08-16T05:13:36.087822Z","pmid":null,"pmcid":null,"fwci":null,"citation_percentile":null,"influential_citations":0,"oa_status":null,"license":null,"views":0,"total_file_size_bytes":0,"version_count":0,"fair_f":null,"fair_a":null,"fair_i":null,"fair_r":null,"fair_zscore":null,"fair_rationale":null,"fair_model":null,"fair_agent_version":null,"fair_fulltext_source":null,"fair_has_llm":null,"fair_computed_at":null,"clinical_trials":[],"software_tools":[],"db_accessions":[],"linked_datasets":[],"topics":[]}