410:
The NOTCH method includes many new, physically-motivated terms compared to the NDDO family of methods, is much less empirical than the other semi-empirical methods (almost all of its parameters are determined non-empirically), provides robust accuracy for bonds between uncommon element combinations,
222:
Within the framework of
Hartree–Fock calculations, some pieces of information (such as two-electron integrals) are sometimes approximated or completely omitted. In order to correct for this loss, semi-empirical methods are parametrized, that is their results are fitted by a set of parameters,
401:, are sometimes classified as semiempirical methods as well. More recent examples include the semiempirical quantum mechanical methods GFNn-xTB (n=0,1,2), which are particularly suited for the geometry, vibrational frequencies, and non-covalent interactions of large molecules.
907:
Michael J. S. Dewar; Eve G. Zoebisch; Eamonn F. Healy; James J. P. Stewart (1985). "Development and use of quantum molecular models. 75. Comparative tests of theoretical procedures for studying chemical reactions".
364:. Here the objective is to use parameters to fit experimental heats of formation, dipole moments, ionization potentials, and geometries. This is by far the largest group of semiempirical methods.
423:
315:. The implementations aimed to fit, not experiment, but ab initio minimum basis set results. These methods are now rarely used but the methodology is often the basis of later methods.
187:
381:. The OMx (x=1,2,3) methods can also be viewed as belonging to this class, although they are also suitable for ground-state applications; in particular, the combination of OM2 and
1257:"GFN2-xTB—An Accurate and Broadly Parametrized Self-Consistent Tight-Binding Quantum Chemical Method with Multipole Electrostatics and Density-Dependent Dispersion Contributions"
285:(PPP), can provide good estimates of the π-electronic excited states, when parameterized well. For many years, the PPP method outperformed ab initio excited state calculations.
215:
for treating large molecules where the full
Hartree–Fock method without the approximations is too expensive. The use of empirical parameters appears to allow some inclusion of
268:
approximation. Their results, however, can be very wrong if the molecule being computed is not similar enough to the molecules in the database used to parametrize the method.
1375:
750:
Pariser, Rudolph; Parr, Robert G. (1953). "A Semi-Empirical Theory of the
Electronic Spectra and Electronic Structure of Complex Unsaturated Molecules. II".
707:
Pariser, Rudolph; Parr, Robert G. (1953). "A Semi-Empirical Theory of the
Electronic Spectra and Electronic Structure of Complex Unsaturated Molecules. I.".
87:
1083:
Nanda, D. N.; Jug, Karl (1980). "SINDO1. A semiempirical SCF MO method for molecular binding energy and geometry I. Approximations and parametrization".
180:
75:
382:
109:
163:
121:
117:
173:
1021:"Optimization of parameters for semiempirical methods VI: More modifications to the NDDO approximations and re-optimization of parameters"
281:
These methods exist for the calculation of electronically excited states of polyenes, both cyclic and linear. These methods, such as the
224:
91:
282:
1126:
Dral, Pavlo O.; Wu, Xin; Spörkel, Lasse; Koslowski, Axel; Weber, Wolfgang; Steiger, Rainer; Scholten, Mirjam; Thiel, Walter (2016).
880:
Michael J. S. Dewar & Walter Thiel (1977). "Ground states of molecules. 38. The MNDO method. Approximations and parameters".
238:
125:
972:"Optimization of parameters for semiempirical methods V: Modification of NDDO approximations and application to 70 elements"
1069:
867:
333:
537:
Hückel, Erich (1932). "Quantentheoretische Beiträge zum
Problem der aromatischen und ungesättigten Verbindungen. III".
155:
45:
211:
formalism, but make many approximations and obtain some parameters from empirical data. They are very important in
151:
139:
53:
1177:"Semiempirical Quantum-Chemical Orthogonalization-Corrected Methods: Benchmarks of Electronically Excited States"
265:
250:
223:
normally in such a way as to produce results that best agree with experimental data, but sometimes to agree with
132:
102:
79:
147:
60:
49:
67:
373:
Methods whose primary aim is to calculate excited states and hence predict electronic spectra. These include
1314:"Development of NOTCH, an all-electron, beyond-NDDO semiempirical method: Application to diatomic molecules"
1128:"Semiempirical Quantum-Chemical Orthogonalization-Corrected Methods: Theory, Implementation, and Parameters"
212:
113:
237:
Semi-empirical methods follow what are often called empirical methods where the two-electron part of the
1325:
759:
716:
673:
597:
546:
503:
452:
216:
30:
651:
341:
95:
38:
1351:
1294:
1237:
1108:
952:
639:
621:
570:
476:
1343:
1286:
1278:
1198:
1157:
1100:
1050:
1001:
935:
James J. P. Stewart (1989). "Optimization of parameters for semiempirical methods I. Method".
810:
775:
732:
689:
613:
562:
519:
468:
202:
208:
1333:
1268:
1229:
1188:
1147:
1139:
1092:
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1032:
991:
983:
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917:
889:
802:
767:
724:
681:
605:
554:
511:
460:
242:
159:
357:
83:
246:
1329:
763:
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601:
550:
507:
456:
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996:
353:
254:
1369:
1355:
1241:
625:
574:
480:
394:
143:
1298:
1112:
956:
1218:"Density-functional tight binding—an approximate density-functional theory method"
1036:
987:
312:
1282:
1273:
1256:
1193:
1176:
1143:
1104:
814:
779:
736:
693:
617:
566:
523:
472:
17:
1020:
971:
664:
Hoffmann, Roald (1963-09-15). "An
Extended HĂĽckel Theory. I. Hydrocarbons".
494:
Hückel, Erich (1931). "Quanstentheoretische Beiträge zum
Benzolproblem II".
1347:
1290:
1202:
1161:
1127:
1073:, Volume 2, Eds. K. B. Lipkowitz and D. B. Boyd, VCH, New York, 313, (1991)
1054:
1005:
948:
870:, Volume 1, Eds. K. B. Lipkowitz and D. B. Boyd, VCH, New York, 45, (1990)
443:
Hückel, Erich (1931). "Quantentheoretische Beiträge zum
Benzolproblem I".
806:
793:
Pople, J. A. (1953). "Electron interaction in unsaturated hydrocarbons".
921:
893:
654:, Molecular Orbital Theory for Organic Chemists, Wiley, New York, (1961)
1096:
609:
588:
HĂĽckel, Erich (1933). "Die freien
Radikale der organischen Chemie IV".
558:
515:
464:
1338:
1313:
1255:
Bannwarth, Christoph; Ehlert, Sebastian; Grimme, Stefan (2019-03-12).
1233:
771:
728:
685:
300:
1217:
378:
374:
345:
329:
325:
241:
is not explicitly included. For π-electron systems, this was the
398:
361:
349:
337:
308:
304:
1175:
Tuna, Deniz; Lu, You; Koslowski, Axel; Thiel, Walter (2016).
596:(9–10). Springer Science and Business Media LLC: 632–668.
545:(9–10). Springer Science and Business Media LLC: 628–648.
424:
List of quantum chemistry and solid-state physics software
385:
is an important tool for excited state molecular dynamics.
502:(5–6). Springer Science and Business Media LLC: 310–337.
451:(3–4). Springer Science and Business Media LLC: 204–286.
260:
Semi-empirical calculations are much faster than their
1091:(2). Springer Science and Business Media LLC: 95–106.
642:, B. O'Leary and R. B. Mallion, Academic Press, 1978.
293:These methods can be grouped into several groups:
844:, Prentice Hall, 4th edition, (1991), pg 579–580
411:and is applicable to ground and excited states.
340:computer programs originally from the group of
181:
8:
289:Methods restricted to all valence electrons.
1216:Seifert, Gotthard; Joswig, Jan-Ole (2012).
264:counterparts, mostly due to the use of the
88:Multi-configurational self-consistent field
1261:Journal of Chemical Theory and Computation
1181:Journal of Chemical Theory and Computation
1132:Journal of Chemical Theory and Computation
801:. Royal Society of Chemistry (RSC): 1375.
397:, e.g. a large family of methods known as
188:
174:
26:
1337:
1272:
1192:
1151:
1044:
995:
910:Journal of the American Chemical Society
882:Journal of the American Chemical Society
249:. For all valence electron systems, the
110:Time-dependent density functional theory
72:Semi-empirical quantum chemistry methods
1376:Semiempirical quantum chemistry methods
857:, Wiley, Chichester, (2002), pg 126–131
435:
131:
101:
59:
37:
29:
937:The Journal of Computational Chemistry
122:Linearized augmented-plane-wave method
118:Orbital-free density functional theory
1222:WIREs Computational Molecular Science
855:Essentials of Computational Chemistry
7:
829:Approximate Molecular Orbital Theory
638:HĂĽckel Theory for Organic Chemists,
1312:Wang, Zikuan; Neese, Frank (2023).
795:Transactions of the Faraday Society
92:Quantum chemistry composite methods
1070:Reviews in Computational Chemistry
868:Reviews in Computational Chemistry
76:Møller–Plesset perturbation theory
25:
277:Methods restricted to π-electrons
672:(6). AIP Publishing: 1397–1412.
1318:The Journal of Chemical Physics
752:The Journal of Chemical Physics
709:The Journal of Chemical Physics
666:The Journal of Chemical Physics
126:Projector augmented wave method
758:(5). AIP Publishing: 767–776.
715:(3). AIP Publishing: 466–471.
1:
1025:Journal of Molecular Modeling
1019:Stewart, James J. P. (2013).
976:Journal of Molecular Modeling
970:Stewart, James J. P. (2007).
272:Preferred application domains
164:Korringa–Kohn–Rostoker method
233:Type of simplifications used
827:J. Pople and D. Beveridge,
156:Empty lattice approximation
1392:
219:effects into the methods.
140:Nearly free electron model
54:Modern valence bond theory
1037:10.1007/s00894-012-1667-x
988:10.1007/s00894-007-0233-4
283:Pariser–Parr–Pople method
266:zero differential overlap
133:Electronic band structure
103:Density functional theory
80:Configuration interaction
1274:10.1021/acs.jctc.8b01176
1194:10.1021/acs.jctc.6b00403
1144:10.1021/acs.jctc.5b01046
324:Methods that are in the
311:that were introduced by
148:Muffin-tin approximation
61:Molecular orbital theory
50:Generalized valence bond
1085:Theoretica Chimica Acta
213:computational chemistry
152:k·p perturbation theory
590:Zeitschrift fĂĽr Physik
539:Zeitschrift fĂĽr Physik
496:Zeitschrift fĂĽr Physik
445:Zeitschrift fĂĽr Physik
251:extended HĂĽckel method
46:Coulson–Fischer theory
949:10.1002/jcc.540100208
395:Tight-binding methods
831:, McGraw–Hill, 1970.
807:10.1039/tf9534901375
217:electron correlation
31:Electronic structure
1330:2023JChPh.158r4102W
922:10.1021/ja00299a024
894:10.1021/ja00457a004
764:1953JChPh..21..767P
721:1953JChPh..21..466P
678:1963JChPh..39.1397H
652:Andrew Streitwieser
602:1933ZPhy...83..632H
551:1932ZPhy...76..628H
508:1931ZPhy...72..310H
457:1931ZPhy...70..204H
96:Quantum Monte Carlo
68:Hartree–Fock method
39:Valence bond theory
1097:10.1007/bf00574898
866:J. J. P. Stewart,
610:10.1007/bf01330865
559:10.1007/bf01341936
516:10.1007/bf01341953
465:10.1007/bf01339530
114:Thomas–Fermi model
1339:10.1063/5.0141686
1234:10.1002/wcms.1094
982:(12): 1173–1213.
916:(13): 3902–3909.
888:(15): 4899–4907.
842:Quantum Chemistry
772:10.1063/1.1699030
729:10.1063/1.1698929
686:10.1063/1.1734456
207:are based on the
203:quantum chemistry
198:
197:
16:(Redirected from
1383:
1360:
1359:
1341:
1309:
1303:
1302:
1276:
1267:(3): 1652–1671.
1252:
1246:
1245:
1213:
1207:
1206:
1196:
1187:(9): 4400–4422.
1172:
1166:
1165:
1155:
1138:(3): 1082–1096.
1123:
1117:
1116:
1080:
1074:
1065:
1059:
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1016:
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299:Methods such as
253:was proposed by
190:
183:
176:
160:GW approximation
27:
21:
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360:, PM6, PM7 and
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279:
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201:Semi-empirical
194:
162:
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124:
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84:Coupled cluster
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70:
52:
48:
23:
22:
15:
12:
11:
5:
1389:
1387:
1379:
1378:
1368:
1367:
1362:
1361:
1324:(18): 184102.
1304:
1247:
1228:(3): 456–465.
1208:
1167:
1118:
1075:
1060:
1011:
962:
943:(2): 209–220.
927:
899:
872:
859:
853:C. J. Cramer,
846:
833:
820:
785:
742:
699:
656:
644:
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255:Roald Hoffmann
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641:
640:C. A. Coulson
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623:
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592:(in German).
591:
584:
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541:(in German).
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498:(in German).
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447:(in German).
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342:Michael Dewar
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243:HĂĽckel method
240:
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145:
144:Tight binding
141:
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127:
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119:
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69:
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58:
55:
51:
47:
44:
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40:
36:
32:
28:
19:
18:Semiempirical
1321:
1317:
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1211:
1184:
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940:
936:
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913:
909:
902:
885:
881:
875:
862:
854:
849:
841:
840:Ira Levine,
836:
828:
823:
798:
794:
788:
755:
751:
745:
712:
708:
702:
669:
665:
659:
647:
634:
593:
589:
583:
542:
538:
532:
499:
495:
489:
448:
444:
438:
344:. These are
292:
280:
261:
259:
247:Erich HĂĽckel
245:proposed by
236:
225:
221:
209:Hartree–Fock
200:
199:
71:
1067:M. Zerner,
1031:(1): 1–32.
239:Hamiltonian
430:References
313:John Pople
1356:258565304
1283:1549-9618
1242:121521740
1105:0040-5744
815:0014-7672
780:0021-9606
737:0021-9606
694:0021-9606
626:121710615
618:1434-6001
575:121787219
567:1434-6001
524:1434-6001
481:186218131
473:1434-6001
262:ab initio
229:results.
226:ab initio
1370:Category
1348:37154284
1299:73419235
1291:30741547
1203:27380455
1162:26771204
1113:98468383
1055:23187683
1006:17828561
957:36907984
418:See also
1326:Bibcode
1153:4785507
1046:3536963
997:2039871
760:Bibcode
717:Bibcode
674:Bibcode
598:Bibcode
547:Bibcode
504:Bibcode
453:Bibcode
336:and/or
334:SPARTAN
205:methods
33:methods
1354:
1346:
1297:
1289:
1281:
1240:
1201:
1160:
1150:
1111:
1103:
1053:
1043:
1004:
994:
955:
813:
778:
735:
692:
624:
616:
573:
565:
522:
479:
471:
301:CNDO/2
1352:S2CID
1295:S2CID
1238:S2CID
1109:S2CID
953:S2CID
622:S2CID
571:S2CID
477:S2CID
379:SINDO
375:ZINDO
346:MINDO
330:AMPAC
326:MOPAC
1344:PMID
1287:PMID
1279:ISSN
1199:PMID
1158:PMID
1101:ISSN
1051:PMID
1002:PMID
811:ISSN
776:ISSN
733:ISSN
690:ISSN
614:ISSN
563:ISSN
520:ISSN
469:ISSN
399:DFTB
383:MRCI
377:and
362:SAM1
350:MNDO
338:CP2K
309:NDDO
307:and
305:INDO
1334:doi
1322:158
1269:doi
1230:doi
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