{"id":"https://openalex.org/W7204958614","doi":"https://doi.org/10.26434/chemrxiv.15008139/v1","title":"Can continuum-solvated DFT resolve the bisulfite protonation-isomer equilibrium? A quantitative benchmark of S- and O-protonated HSO3","display_name":"Can continuum-solvated DFT resolve the bisulfite protonation-isomer equilibrium? A quantitative benchmark of S- and O-protonated HSO3","publication_year":2026,"publication_date":"2026-09-01","ids":{"openalex":"https://openalex.org/W7204958614","doi":"https://doi.org/10.26434/chemrxiv.15008139/v1"},"language":"en","primary_location":{"id":"doi:10.26434/chemrxiv.15008139/v1","doi":"https://doi.org/10.26434/chemrxiv.15008139/v1","is_oa":true,"landing_page_url":"https://doi.org/10.26434/chemrxiv.15008139/v1","pdf_url":"https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15008139/v1","source":{"id":"https://openalex.org/S4393918830","display_name":"ChemRxiv","issn_l":"2573-2293","issn":["2573-2293"],"is_oa":false,"is_in_doaj":false,"is_core":false,"listed_in":[],"host_organization":null,"host_organization_name":null,"host_organization_lineage":[],"host_organization_lineage_names":[],"type":"repository"},"license":"cc-by","license_id":"https://openalex.org/licenses/cc-by","version":"acceptedVersion","is_accepted":true,"is_published":false,"raw_source_name":null,"raw_type":"posted-content"},"volume":null,"type":"preprint","is_traditional":true,"indexed_in":["crossref"],"open_access":{"is_oa":true,"oa_status":"green","oa_url":"https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15008139/v1","any_repository_has_fulltext":true},"authorships":[{"author_position":"first","author":{"id":"https://openalex.org/A5143475636","display_name":"Aris Tsai","orcid":"https://orcid.org/0009-0004-8641-7647","observed_orcids":["https://orcid.org/0009-0004-8641-7647"]},"institutions":[{"id":"https://openalex.org/I97018004","display_name":"Stanford University","ror":"https://ror.org/00f54p054","country_code":"US","type":"education","lineage":["https://openalex.org/I97018004"]}],"countries":["US"],"is_corresponding":true,"raw_author_name":"Aris Tsai","raw_affiliation_strings":["Affiliations Chemistry , Stanford Online High School , Stanford University , Stanford , California , USA"],"raw_orcid":"https://orcid.org/0009-0004-8641-7647","affiliations":[{"raw_affiliation_string":"Affiliations Chemistry , Stanford Online High School , Stanford University , Stanford , California , USA","institution_ids":["https://openalex.org/I97018004"]}]}],"institutions":[],"countries_distinct_count":1,"institutions_distinct_count":1,"corresponding_author_ids":["https://openalex.org/A5143475636"],"corresponding_institution_ids":["https://openalex.org/I97018004"],"apc_list":null,"apc_paid":null,"fwci":null,"has_fulltext":true,"cited_by_count":0,"citation_normalized_percentile":null,"cited_by_percentile_year":null,"biblio":{"volume":null,"issue":null,"first_page":null,"last_page":null},"is_retracted":false,"is_paratext":false,"is_xpac":false,"primary_topic":{"id":"https://openalex.org/T10002","display_name":"Advanced Chemical Physics Studies","score":0.9951000213623047,"subfield":{"id":"https://openalex.org/subfields/3107","display_name":"Atomic and Molecular Physics, and Optics"},"field":{"id":"https://openalex.org/fields/31","display_name":"Physics and Astronomy"},"domain":{"id":"https://openalex.org/domains/3","display_name":"Physical Sciences"}},"topics":[{"id":"https://openalex.org/T10002","display_name":"Advanced Chemical Physics Studies","score":0.9951000213623047,"subfield":{"id":"https://openalex.org/subfields/3107","display_name":"Atomic and Molecular Physics, and Optics"},"field":{"id":"https://openalex.org/fields/31","display_name":"Physics and Astronomy"},"domain":{"id":"https://openalex.org/domains/3","display_name":"Physical Sciences"}},{"id":"https://openalex.org/T11177","display_name":"Spectroscopy and Quantum Chemical Studies","score":0.002199999988079071,"subfield":{"id":"https://openalex.org/subfields/3107","display_name":"Atomic and Molecular Physics, and Optics"},"field":{"id":"https://openalex.org/fields/31","display_name":"Physics and Astronomy"},"domain":{"id":"https://openalex.org/domains/3","display_name":"Physical Sciences"}},{"id":"https://openalex.org/T12191","display_name":"Physical Organic Chemistry and Reaction Kinetics","score":0.0012000000569969416,"subfield":{"id":"https://openalex.org/subfields/1605","display_name":"Organic Chemistry"},"field":{"id":"https://openalex.org/fields/16","display_name":"Chemistry"},"domain":{"id":"https://openalex.org/domains/3","display_name":"Physical Sciences"}}],"keywords":[{"id":"https://openalex.org/keywords/bisulfite","display_name":"bisulfite","score":0.8569999933242798},{"id":"https://openalex.org/keywords/implicit-solvent-models","display_name":"implicit solvent","score":0.5860000252723694},{"id":"https://openalex.org/keywords/basis-set-convergence","display_name":"basis set convergence","score":0.8159999847412109},{"id":"https://openalex.org/keywords/density-functional-theory-benchmarking","display_name":"density functional benchmarking","score":0.4620000123977661},{"id":"https://openalex.org/keywords/temperature-dependent-equilibrium","display_name":"temperature-dependent equilibrium","score":0.36500000953674316}],"concepts":[{"id":"https://openalex.org/C185592680","wikidata":"https://www.wikidata.org/wiki/Q2329","display_name":"Chemistry","level":0,"score":0.5561000108718872},{"id":"https://openalex.org/C147597530","wikidata":"https://www.wikidata.org/wiki/Q369472","display_name":"Computational chemistry","level":1,"score":0.4738999903202057},{"id":"https://openalex.org/C3288061","wikidata":"https://www.wikidata.org/wiki/Q161064","display_name":"Enthalpy","level":2,"score":0.4133000075817108},{"id":"https://openalex.org/C18705241","wikidata":"https://www.wikidata.org/wiki/Q1128023","display_name":"Conformational isomerism","level":3,"score":0.39559999108314514},{"id":"https://openalex.org/C124681953","wikidata":"https://www.wikidata.org/wiki/Q339062","display_name":"Decomposition","level":2,"score":0.3750999867916107},{"id":"https://openalex.org/C184651966","wikidata":"https://www.wikidata.org/wiki/Q906356","display_name":"Aqueous solution","level":2,"score":0.3549000024795532},{"id":"https://openalex.org/C186633575","wikidata":"https://www.wikidata.org/wiki/Q845060","display_name":"Maxima and minima","level":2,"score":0.3506999909877777},{"id":"https://openalex.org/C145148216","wikidata":"https://www.wikidata.org/wiki/Q36496","display_name":"Ion","level":2,"score":0.34299999475479126},{"id":"https://openalex.org/C86025842","wikidata":"https://www.wikidata.org/wiki/Q5358432","display_name":"Electronic structure","level":2,"score":0.31709998846054077},{"id":"https://openalex.org/C102931765","wikidata":"https://www.wikidata.org/wiki/Q189673","display_name":"Dissociation (chemistry)","level":2,"score":0.3133000135421753},{"id":"https://openalex.org/C147789679","wikidata":"https://www.wikidata.org/wiki/Q11372","display_name":"Physical chemistry","level":1,"score":0.3070000112056732},{"id":"https://openalex.org/C22693506","wikidata":"https://www.wikidata.org/wiki/Q3075290","display_name":"Hybrid functional","level":3,"score":0.28189998865127563},{"id":"https://openalex.org/C2781442258","wikidata":"https://www.wikidata.org/wiki/Q46310","display_name":"Ab initio","level":2,"score":0.2705000042915344},{"id":"https://openalex.org/C84551667","wikidata":"https://www.wikidata.org/wiki/Q155640","display_name":"Potential energy","level":2,"score":0.2671999931335449},{"id":"https://openalex.org/C2779953032","wikidata":"https://www.wikidata.org/wiki/Q305364","display_name":"Thiophene","level":2,"score":0.26600000262260437},{"id":"https://openalex.org/C192562407","wikidata":"https://www.wikidata.org/wiki/Q228736","display_name":"Materials science","level":0,"score":0.25600001215934753},{"id":"https://openalex.org/C184779094","wikidata":"https://www.wikidata.org/wiki/Q26383","display_name":"Atomic physics","level":1,"score":0.25049999356269836}],"mesh":[],"locations_count":1,"locations":[{"id":"doi:10.26434/chemrxiv.15008139/v1","doi":"https://doi.org/10.26434/chemrxiv.15008139/v1","is_oa":true,"landing_page_url":"https://doi.org/10.26434/chemrxiv.15008139/v1","pdf_url":"https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15008139/v1","source":{"id":"https://openalex.org/S4393918830","display_name":"ChemRxiv","issn_l":"2573-2293","issn":["2573-2293"],"is_oa":false,"is_in_doaj":false,"is_core":false,"listed_in":[],"host_organization":null,"host_organization_name":null,"host_organization_lineage":[],"host_organization_lineage_names":[],"type":"repository"},"license":"cc-by","license_id":"https://openalex.org/licenses/cc-by","version":"acceptedVersion","is_accepted":true,"is_published":false,"raw_source_name":null,"raw_type":"posted-content"}],"best_oa_location":{"id":"doi:10.26434/chemrxiv.15008139/v1","doi":"https://doi.org/10.26434/chemrxiv.15008139/v1","is_oa":true,"landing_page_url":"https://doi.org/10.26434/chemrxiv.15008139/v1","pdf_url":"https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15008139/v1","source":{"id":"https://openalex.org/S4393918830","display_name":"ChemRxiv","issn_l":"2573-2293","issn":["2573-2293"],"is_oa":false,"is_in_doaj":false,"is_core":false,"listed_in":[],"host_organization":null,"host_organization_name":null,"host_organization_lineage":[],"host_organization_lineage_names":[],"type":"repository"},"license":"cc-by","license_id":"https://openalex.org/licenses/cc-by","version":"acceptedVersion","is_accepted":true,"is_published":false,"raw_source_name":null,"raw_type":"posted-content"},"sustainable_development_goals":[],"study_designs":[],"awards":[],"funders":[],"has_content":{"grobid_xml":true,"pdf":true},"content_urls":{"pdf":"https://content.openalex.org/works/W7204958614.pdf","grobid_xml":"https://content.openalex.org/works/W7204958614.grobid-xml"},"referenced_works_count":10,"referenced_works":["https://openalex.org/W28713913","https://openalex.org/W1988091937","https://openalex.org/W2008423326","https://openalex.org/W2011215428","https://openalex.org/W2029448125","https://openalex.org/W2037570317","https://openalex.org/W2143981217","https://openalex.org/W2761808733","https://openalex.org/W3193988690","https://openalex.org/W4403482196"],"related_works":["https://openalex.org/W2060132833","https://openalex.org/W2144787512","https://openalex.org/W2161257125","https://openalex.org/W3138328478","https://openalex.org/W1575039830","https://openalex.org/W4250757513","https://openalex.org/W2079200771","https://openalex.org/W2062832760","https://openalex.org/W2811076169","https://openalex.org/W2036428827"],"abstract_inverted_index":{"The":[0,211],"aqueous":[1],"bisulfite":[2],"anion":[3],"supports":[4],"experimentally":[5,221],"established":[6],"S-":[7],"and":[8,40,45,50,57,154,177],"O-protonated":[9,73,84],"isomers":[10],"whose":[11],"relative":[12],"populations":[13],"vary":[14],"with":[15,167],"temperature,":[16],"making":[17],"the":[18,83,100,104,111,117,126,130,141,162,183,204,232,238],"pair":[19],"a":[20,76,95],"compact":[21],"test":[22],"of":[23],"solution-phase":[24],"electronic-structure":[25],"methods.":[26],"We":[27],"carried":[28],"out":[29],"46":[30],"independent":[31],"Q-Chem":[32],"6.2":[33],"calculations":[34,56],"spanning":[35],"conformer":[36],"generation,":[37],"B3LYP,":[38,150],"PBE0":[39,153],"\u03c9B97X-D,":[41,157],"diffuse":[42],"double-,":[43],"triple-":[44],"quadruple-\u03b6":[46],"basis":[47,121],"sets,":[48],"SMD":[49,132],"PCM":[51],"water,":[52],"gas-phase":[53],"controls,":[54],"frequency":[55],"temperature-dependent":[58,241],"thermochemistry.":[59],"Four":[60],"S-protonated":[61,112],"starts":[62,74],"collapsed":[63],"to":[64,106,125,182,198,209,222],"one":[65],"minimum":[66,85],"within":[67],"0.035":[68],"kcal":[69,78,88,108,119,137,147,175,219,224],"mol-1,":[70,109],"whereas":[71,203],"four":[72],"formed":[75],"0.412":[77],"mol-1":[79,89,120,148,176,220,225],"manifold.":[80],"At":[81],"B3LYP/def2-SVPD/SMD,":[82],"was":[86],"12.11":[87],"lower":[90],"in":[91],"electronic":[92,128,165],"energy,":[93],"but":[94],"def2-TZVPD":[96],"single-point":[97],"comparison":[98],"on":[99],"selected":[101],"minima":[102],"inverted":[103],"ordering":[105],"+0.641":[107],"favoring":[110],"isomer.":[113],"Energy":[114],"decomposition":[115],"localized":[116],"12.75":[118],"shift":[122],"almost":[123],"entirely":[124],"intrinsic":[127],"term;":[129],"differential":[131],"polarization":[133],"remained":[134],"near":[135],"\u22125.46":[136],"mol-1.":[138],"def2-QZVPD":[139],"changed":[140],"O\u2212S":[142],"gap":[143],"by":[144],"only":[145],"0.008":[146],"for":[149,152,156],"0.016":[151],"\u22120.073":[155],"establishing":[158],"triple-\u03b6":[159],"convergence.":[160],"Combining":[161],"basis-converged":[163],"B3LYP":[164],"energy":[166],"validated":[168],"qRRHO":[169],"corrections":[170],"gave":[171],"\u0394G298":[172],"=":[173,179,186,193],"\u22120.473":[174],"Qi":[178,185,192],"2.22,":[180],"close":[181],"experimental":[184],"2.67.":[187],"However,":[188],"experiment":[189],"decreases":[190],"from":[191,207,217],"3.31":[194],"at":[195,200],"278":[196],"K":[197],"1.63":[199],"358":[201],"K,":[202],"calculation":[205],"increases":[206],"2.03":[208],"2.54.":[210],"associated":[212],"effective":[213],"enthalpy":[214],"changes":[215],"sign,":[216],"\u22121.746":[218],"+0.550":[223],"computationally.":[226],"Continuum-solvated":[227],"DFT":[228],"can":[229],"therefore":[230],"reproduce":[231],"room-temperature":[233],"equilibrium":[234],"fortuitously":[235],"while":[236],"failing":[237],"more":[239],"stringent":[240],"benchmark.":[242]},"counts_by_year":[],"updated_date":"2026-11-04T10:54:05.112534","created_date":"2026-09-02T00:00:00"}