A DFT and TD-DFT Study of Two Hydralazine Derivatives for Organic Solar Cells and Nonlinear Optical Applications

<table class="table-group" id="tab10"><tr><td><table class="table"><tr><td class="thead-hr" colspan="8"><hr/></td></tr><tr class="thead"><td class="align_left">Level of theory</td><td class="align_center">Molecule</td><td class="align_center">Excited state</td><td class="align_center">Coefficient + MO</td><td class="align_center"><span style="width: 24.4821ptpx;"><svg height="12.584pt" id="M90" style="vertical-align:-3.29567pt" version="1.1" viewbox="-0.0498162 -9.28833 24.4821 12.584" width="24.4821pt" xmlns="http://www.w3.org/2000/svg" xmlns:xlink="http://www.w3.org/1999/xlink"><g transform="matrix(.013,0,0,-0.013,0,0)"><path d="M529 97L508 118C475 75 449 58 438 58C428 58 421 66 415 104C393 234 374 403 364 496C345 670 307 712 254 712C220 712 174 691 153 669L161 645C176 653 194 658 206 658C237 658 261 640 278 562C287 522 290 483 293 434C223 269 110 105 23 9L32 -12C59 -6 85 0 108 7C152 64 251 252 300 366C307 297 315 221 337 82C346 24 363 -12 393 -12C425 -12 475 13 529 97Z"></path></g><g transform="matrix(.0091,0,0,-0.0091,7.761,3.132)"><path d="M810 0V30C751 35 744 40 744 106V296C744 396 694 451 614 451C583 451 558 438 537 425C512 409 485 391 454 368C434 420 390 451 342 451C309 451 285 439 260 424C228 405 206 387 185 372V453C141 434 90 421 43 413V386C102 378 105 373 105 309V106C105 41 96 35 29 30V0H243V30C194 35 185 41 185 106V335C216 360 256 389 297 389C357 389 384 348 384 275V106C384 41 374 35 312 30V0H530V30C475 35 465 41 465 104V294C465 313 464 324 463 336C502 367 539 389 576 389C637 389 663 346 663 274V109C663 41 653 35 593 30V0H810Z"></path></g><g transform="matrix(.0091,0,0,-0.0091,15.323,3.132)"><path d="M442 39L431 68C420 63 406 57 394 57C377 57 359 71 359 118V301C359 353 349 393 314 424C291 443 261 451 230 451C171 438 107 401 79 381C59 366 46 355 46 340C46 316 72 295 91 295C106 295 117 303 122 319C131 350 139 371 152 384C163 397 178 404 197 404C246 404 281 365 281 293V278C260 262 186 232 124 213C69 194 41 161 41 112C41 47 92 -12 163 -12C195 -12 243 25 283 51C288 35 293 22 308 7C319 -4 339 -12 354 -12L442 39ZM281 87C262 68 226 51 199 51C169 51 129 74 129 126C129 162 151 181 190 198C211 208 259 229 281 240V87Z"></path></g><g transform="matrix(.0091,0,0,-0.0091,19.409,3.132)"><path d="M482 0V30C420 38 407 48 370 103L273 248C308 299 331 332 352 357C387 397 401 404 463 409V439H277V409C318 405 324 400 307 369C290 337 270 307 251 279L194 367C175 396 180 402 220 409V439H18V409C74 401 87 395 117 349L204 213C173 168 147 130 119 95C78 46 67 38 5 30V0H195V30C144 38 143 47 162 79C181 112 202 149 225 181L297 70C314 43 307 35 264 30V0H482Z"></path></g></svg></span></td><td class="align_center"><i>E</i><sub>abs</sub></td><td class="align_center"><span style="width: 24.5709ptpx;"><svg height="12.7178pt" id="M91" style="vertical-align:-3.42947pt" version="1.1" viewbox="-0.0498162 -9.28833 24.5709 12.7178" width="24.5709pt" xmlns="http://www.w3.org/2000/svg" xmlns:xlink="http://www.w3.org/1999/xlink"><g transform="matrix(.013,0,0,-0.013,0,0)"><path d="M619 670C619 686 593 712 555 712S459 686 410 634S335 504 320 430H250L219 400L222 388H312L258 73C223 -133 201 -166 187 -180C175 -191 158 -199 140 -199C123 -199 88 -188 74 -172C68 -166 63 -164 54 -171C38 -185 23 -201 23 -215C23 -236 60 -261 93 -261C122 -261 161 -247 207 -200C268 -138 300 -71 337 94C365 220 376 277 394 387L501 399L521 430H401C432 623 464 665 501 665C524 665 544 651 567 627C577 617 583 618 592 625C601 631 619 651 619 670Z"></path></g><g transform="matrix(.0091,0,0,-0.0091,6.721,3.132)"><path d="M381 665C170 665 44 498 44 318C44 125 188 -15 369 -15C552 -15 703 117 703 333C703 534 550 665 381 665ZM359 629C491 629 601 517 601 306C601 114 502 21 390 21C249 21 146 158 146 346S248 629 359 629Z"></path></g><g transform="matrix(.0091,0,0,-0.0091,13.519,3.132)"><path d="M409 504C401 567 396 607 392 642C354 654 312 665 266 665C137 665 60 583 60 487C60 374 161 325 225 290C300 250 355 215 355 141C355 68 311 21 235 21C131 21 86 122 71 183L41 176C48 128 61 42 68 21C78 16 93 8 118 0C142 -7 175 -15 216 -15C349 -15 438 69 438 174C438 287 344 333 265 374C186 414 138 449 138 522C138 576 172 631 249 631C336 631 363 562 380 499L409 504Z"></path></g><g transform="matrix(.0091,0,0,-0.0091,17.832,3.132)"><path d="M614 175C564 76 510 21 408 21C256 21 146 149 146 336C146 488 235 629 402 629C510 629 570 586 597 480L626 488C620 541 614 582 606 638C578 643 510 665 429 665C206 665 44 527 44 316C44 157 153 -15 402 -15C474 -15 558 5 586 11C604 45 629 119 643 165L614 175Z"></path></g></svg></span></td><td class="align_center"><span style="width: 24.5269ptpx;"><svg height="8.57479pt" id="M92" style="vertical-align:-0.04981041pt" version="1.1" viewbox="-0.0498162 -8.52498 24.5269 8.57479" width="24.5269pt" xmlns="http://www.w3.org/2000/svg" xmlns:xlink="http://www.w3.org/1999/xlink"><g transform="matrix(.013,0,0,-0.013,0,0)"><path d="M495 163C480 117 462 85 444 65C421 39 387 34 332 34C290 34 256 36 236 47C218 57 213 77 213 131V526C213 612 222 616 301 622V650H40V622C122 616 128 611 128 526V126C128 41 120 34 36 28V0H489C498 31 519 126 525 157L495 163Z"></path></g><g transform="matrix(.013,0,0,-0.013,6.994,0)"><path d="M729 650H468V622C546 615 554 610 554 527V365H213V527C213 610 221 616 297 622V650H38V622C120 616 128 611 128 527V123C128 39 120 34 40 28V0H303V28C221 34 213 40 213 123V322H554V123C554 39 546 34 460 28V0H728V28C647 34 639 39 639 123V527C639 610 647 615 729 622V650Z"></path></g><g transform="matrix(.013,0,0,-0.013,16.952,0)"><path d="M517 162C503 123 484 88 467 68C445 42 417 34 341 34C291 34 256 34 237 47C219 59 213 81 213 128V317H308C395 317 402 311 415 240H444V431H415C403 364 398 356 307 356H213V584C213 613 215 616 246 616H322C394 616 421 609 435 587C448 566 458 544 467 502L496 506C493 557 488 625 488 650H42V622C120 616 128 612 128 523V125C128 43 120 35 29 28V0H511C520 31 540 125 546 158L517 162Z"></path></g></svg></span></td></tr><tr><td class="thead-hr" colspan="8"><hr/></td></tr><tr><td class="align_left" rowspan="2">CAM-B3LYP</td><td class="align_center">PEPH</td><td class="align_center">S<sub>0</sub> ⟶ S<sub>1</sub></td><td class="align_center">H ⟶ L (82.58)</td><td class="align_center">312.2</td><td class="align_center">3.971</td><td class="align_center">0.3617</td><td class="align_center">0.5652</td></tr><tr><td class="align_center">PPEH</td><td class="align_center">S<sub>0</sub> ⟶ S<sub>1</sub></td><td class="align_center">H ⟶ L (84.29)</td><td class="align_center">314.6</td><td class="align_center">3.941</td><td class="align_center">0.3923</td><td class="align_center">0.5947</td></tr><tr><td class="align_left" colspan="8"><hr/></td></tr><tr><td class="align_left" rowspan="2"><svg height="6.1673pt" id="M93" style="vertical-align:-0.2063904pt" version="1.1" viewbox="-0.0498162 -5.96091 8.42472 6.1673" width="8.42472pt" xmlns="http://www.w3.org/2000/svg" xmlns:xlink="http://www.w3.org/1999/xlink"><g transform="matrix(.013,0,0,-0.013,0,0)"><path d="M615 290C615 392 563 448 529 448C511 448 491 441 484 434L483 425C518 400 546 349 546 273C546 158 504 46 417 46C381 46 356 77 356 142C356 184 380 293 392 334L387 340L307 323C305 288 296 228 287 188C265 94 221 52 180 52C144 52 112 89 112 171C112 278 164 372 241 430L226 454C106 394 23 288 23 155C23 40 79 -12 139 -12C184 -12 245 32 285 85C292 31 322 -12 376 -12C423 -12 470 18 501 45C570 104 615 184 615 290Z"></path></g></svg> B97-XD</td><td class="align_center">PEPH</td><td class="align_center">S<sub>0</sub> ⟶ S<sub>1</sub></td><td class="align_center">H ⟶ L (77.21)</td><td class="align_center">300.5</td><td class="align_center">4.126</td><td class="align_center">0.3552</td><td class="align_center">0.5586</td></tr><tr><td class="align_center">PPEH</td><td class="align_center">S<sub>0</sub> ⟶ S<sub>1</sub></td><td class="align_center">H ⟶ L (74.15)</td><td class="align_center">303.7</td><td class="align_center">4.082</td><td class="align_center">0.3307</td><td class="align_center">0.5330</td></tr><tr class="table-tr"><td colspan="8"><hr class="tbody-hr"/></td></tr></table></td></tr><tr class="table-fn"><td><div><i>E</i><sub>abs</sub> ⟶ excitation energies (in eV), <svg height="12.5612pt" id="M94" style="vertical-align:-3.27287pt" version="1.1" viewbox="-0.0498162 -9.28833 20.317 12.5612" width="20.317pt" xmlns="http://www.w3.org/2000/svg" xmlns:xlink="http://www.w3.org/1999/xlink"><g transform="matrix(.013,0,0,-0.013,0,0)"><path d="M529 97L508 118C475 75 449 58 438 58C428 58 421 66 415 104C393 234 374 403 364 496C345 670 307 712 254 712C220 712 174 691 153 669L161 645C176 653 194 658 206 658C237 658 261 640 278 562C287 522 290 483 293 434C223 269 110 105 23 9L32 -12C59 -6 85 0 108 7C152 64 251 252 300 366C307 297 315 221 337 82C346 24 363 -12 393 -12C425 -12 475 13 529 97Z"></path></g><g transform="matrix(.0091,0,0,-0.0091,7.761,3.132)"><path d="M433 39L423 65C413 59 399 54 387 54C370 54 352 69 352 114V299C352 352 342 392 307 422C285 440 255 449 225 449C168 437 102 399 75 379C56 365 44 353 44 339C44 315 69 296 87 296C101 296 111 303 116 319C124 349 133 371 145 385C156 397 171 404 190 404C241 404 275 364 275 291V274C253 256 180 229 120 209C65 190 39 159 39 110C39 47 88 -12 159 -12C189 -12 237 25 277 52C282 35 288 21 301 8C312 -3 333 -12 348 -12L433 39ZM275 84C256 65 221 48 195 48C164 48 124 73 124 124C124 161 146 180 185 198C206 208 254 229 275 240V84Z"></path></g><g transform="matrix(.0091,0,0,-0.0091,11.683,3.132)"><path d="M152 404V712C115 698 54 683 7 677V654C71 648 73 642 73 579V24C128 -2 179 -12 220 -12C353 -12 471 92 471 238C471 357 381 449 274 449C262 449 249 446 233 439L152 404ZM152 374C170 384 202 393 230 393C313 393 382 326 382 213C382 97 330 26 246 26C194 26 165 62 158 81C154 91 152 101 152 116V374Z"></path></g><g transform="matrix(.0091,0,0,-0.0091,16.306,3.132)"><path d="M319 325C317 349 306 409 297 431C277 440 250 449 209 449C117 449 57 389 57 319C57 243 122 209 182 182C232 159 261 135 261 91C261 48 227 21 190 21C130 21 85 79 68 145L41 140C41 104 51 36 58 22C75 7 121 -12 172 -12C252 -12 337 35 337 126C337 195 286 231 210 262C166 281 126 304 126 348C126 388 152 417 191 417C240 417 274 378 294 318L319 325Z"></path></g></svg> ⟶ wavelengths (in nm), ƒ ⟶ oscillator strengths, MO ⟶ molecular orbital coefficients, H ⟶ HOMO, L ⟶ LUMO, LHE ⟶ light harvesting efficiencies.<br/></div></td></tr></table>

<div>Absorption wavelength, highest oscillator strength, main transitions (in %), and light harvesting efficiencies of PEPH and PPEH computed at CAM-B3LYP/def2-tzvpp and <svg height="6.1673pt" id="M89" style="vertical-align:-0.2063904pt" version="1.1" viewbox="-0.0498162 -5.96091 8.42472 6.1673" width="8.42472pt" xmlns="http://www.w3.org/2000/svg" xmlns:xlink="http://www.w3.org/1999/xlink"><g transform="matrix(.013,0,0,-0.013,0,0)"><path d="M615 290C615 392 563 448 529 448C511 448 491 441 484 434L483 425C518 400 546 349 546 273C546 158 504 46 417 46C381 46 356 77 356 142C356 184 380 293 392 334L387 340L307 323C305 288 296 228 287 188C265 94 221 52 180 52C144 52 112 89 112 171C112 278 164 372 241 430L226 454C106 394 23 288 23 155C23 40 79 -12 139 -12C184 -12 245 32 285 85C292 31 322 -12 376 -12C423 -12 470 18 501 45C570 104 615 184 615 290Z"></path></g></svg> B97-XD/def2-tzvpp levels of theory.</div>

Journal of Chemistry

tab10

Table 10

Table 10: A DFT and TD-DFT Study of Two Hydralazine Derivatives for Organic Solar Cells and Nonlinear Optical Applications 