Computational Chemistry

origin of, 87–91
SCRF.Seeself-consistent reaction field
secular determinants, 149
secular equations, 123, 145–7, 149–53, 166, 167
self-consistent field (SCF) method, 177–81,
195, 196, 203, 205, 206, 212, 215,
223–38, 229, 231, 244, 245, 248, 255,
259, 262, 273
self-consistent reaction field (SCRF), 527
semiempirical, 3–5, 14, 60–4, 67, 71, 73, 74,
76, 85, 102, 129, 145, 155, 163–5, 167,
176, 197, 206, 222, 233, 239, 242, 243,
253, 255, 281, 293, 304, 311, 312, 321,
324, 326, 360, 372, 391–438, 445–7,
461, 466, 468, 474, 477, 483–6, 492,
493, 495, 496, 497, 509, 510, 511, 527,
535, 542, 549, 551, 552, 566, 574,
575, 580
semilocal, 462, 466
shape, and Born-Oppenheimer approximation,
21–3
SHM.Seesimple H€uckel method
SIESTA program for large systems, 551
simple harmonic oscillator, 10
simple H€uckel method (SHM), 86, 102, 103,
107, 118–46, 152–3, 155, 163–6
applications, 102–52, 166
derivation, 118–20
software, 580–1
single point calculations, 213, 229, 265, 266,
274, 275, 312
singlet diradicals, 258, 291, 521–53
size-consistency, 276–7
Slater, 181–6, 188, 189, 194, 196, 199, 201,
203, 214, 232–6, 238, 256, 264, 269,
270, 291, 342, 373, 539, 540
determinant, 181–4, 186, 189, 194, 196,
199, 201, 203, 232, 264, 269, 270, 291,
342, 373, 395, 447, 454, 455, 496, 511
functions, 214, 233–6, 238, 239, 245, 395,
399, 405, 408
SN2 reaction
continuum solvation, 523
microsolvation/explicit solvation, 522–4,
527, 531
softness, 491–509, 512
software, for computational chemistry, 577,
578, 582
solvation, 521–53
explicit, 522, 523, 534, 553
explicit (micro-), 522, 523, 534
solvent, 522–6, 531, 532, 534, 537, 553
solvent-accessible surface area (SASA), 525

SPARTAN (software), 64, 72, 238, 242, 265,

301, 326, 408, 409, 430, 434, 468, 478,

480, 527, 528, 530, 552, 575, 581

spatial orbitals, 181–4, 186, 188, 192, 194, 196,

232, 373

spectra, 1, 2, 4, 5

spectra, calculated

by ab initio methods, 332–7

by density functional methods, 446, 484

by molecular mechanics methods, 72–3

by semiempirical methods, 423–6

spin, electron, 97, 145, 188, 196, 354,

446, 511

spin orbitals, 181–5, 188, 194, 270, 271, 273,

311, 373

spin-orbit coupling, 258, 287, 548, 549

static correlation, 258, 274, 543

stationary points, 13–21, 24–6, 29, 30–6, 39,

72, 79, 293, 332, 333, 337, 355, 367,

401, 500, 524, 537, 538, 539

stereomutation, 538

Stewart, J.J.P., 408, 410–2, 433

strain, 304–8, 359

SVWN functional, 462

symmetry, 11, 36–9

T

TDDFT, 491–3, 511

tessellations, 525

tesserae, 525

tetramethylene (1,4-butanediyl), 535,

537, 538

thermodynamics, 267, 292–4, 297, 298,

303–23, 326, 339

calculating reaction energies, 267, 297,

303–32, 420–3, 477–84

Thomas-Fermi, 448, 462

Thomas-Fermi-Dirac, 448

Thomas, L.H., 448

Thomson, J.J. Sir, 93, 94

times for calculations, 275, 276, 480, 483, 491,

492, 509

TPSS functional, 460, 482

transition metals, 521–53

transition state (transition structure), 17

transition state, criteria for, 40

transition structure (transition state), 17

trimethylene (1,3-propanediyl), 536–8

triquinacene, 570–2

U

ultraviolet catastrophe, 88

unrestricted HF (UHF), 196, 232, 288

Index 663