Strongly Bound Frenkel Excitons on TiO<sub>2</sub> Nanoparticles: An Evolutionary and DFT Approach

<div>Properties of TiO<sub>2</sub> NPs obtained at the PBE0/def2-TZVP level of theory as a function of the cluster size <span class="nowrap"><svg height="6.1673pt" id="M103" style="vertical-align:-0.2063904pt" version="1.1" viewbox="-0.0498162 -5.96091 6.6501 6.1673" width="6.6501pt" 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 86L479 114C446 82 419 66 409 66C401 66 401 72 406 97C420 166 436 231 453 297C489 435 454 448 428 448C406 448 384 439 354 422C305 394 222 327 161 247H159L183 345C200 415 194 448 173 448C143 448 82 410 23 351L38 325C64 349 95 371 105 371C111 371 116 365 109 336L25 -4L31 -12C50 -4 77 3 107 9C119 69 132 122 145 168C197 254 321 381 370 381C387 381 393 374 378 305L329 95C309 17 320 -12 345 -12C372 -12 430 19 495 86Z"></path></g></svg>.</span> (a) Average <svg height="11.5564pt" id="M104" style="vertical-align:-2.26807pt" version="1.1" viewbox="-0.0498162 -9.28833 44.2436 11.5564" width="44.2436pt" 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="M530 686C535 705 530 712 521 712C504 712 448 684 359 674L358 648H393C437 648 439 646 429 593L400 435C372 447 345 448 332 448C286 448 194 414 144 373C68 311 23 203 23 111C23 26 57 -12 91 -12C120 -12 147 3 188 29C227 54 290 102 341 170H343L322 71C308 6 320 -12 341 -12C373 -12 442 27 501 96L485 120C455 91 422 67 408 67C401 67 401 76 404 91C440 294 479 473 530 686ZM387 375L355 241C326 187 200 53 142 53C126 53 109 73 109 130C109 217 154 337 218 381C240 396 265 404 297 404S372 390 387 375Z"></path></g><g transform="matrix(.013,0,0,-0.013,7.215,0)"><path d="M300 -147C201 -63 143 98 143 270S200 602 300 686L282 710C136 610 70 450 70 271V270C70 89 136 -72 282 -170L300 -147Z"></path></g><g transform="matrix(.013,0,0,-0.013,11.713,0)"><path d="M592 498C586 556 582 629 581 675H560C545 656 537 650 510 650H115C87 650 74 652 60 675H40C38 620 33 555 28 495H57C69 539 77 568 89 585C102 607 122 616 205 616H267V123C267 44 259 34 168 28V0H454V28C360 34 352 44 352 123V616H422C498 616 514 608 531 584C542 568 552 543 562 495L592 498Z"></path></g><g transform="matrix(.013,0,0,-0.013,19.526,0)"><path d="M135 536C164 536 186 560 186 587C186 617 164 639 136 639C109 639 85 617 85 587C85 560 109 536 135 536ZM252 0V26C188 32 181 38 181 106V451C138 433 90 420 39 412V388C99 379 102 374 102 312V106C102 38 95 32 32 26V0H252Z"></path></g><g transform="matrix(.013,0,0,-0.013,23.053,0)"><path d="M469 201V252H50V201H469Z"></path></g><g transform="matrix(.013,0,0,-0.013,29.838,0)"><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(.013,0,0,-0.013,39.585,0)"><path d="M275 270C275 450 212 609 64 710L45 686C145 604 203 442 203 270S147 -63 45 -147L64 -170C213 -68 275 89 275 270Z"></path></g></svg> bond length; (b) volume for the ground state of <span class="nowrap"><svg height="12.5794pt" id="M105" style="vertical-align:-3.29107pt" version="1.1" viewbox="-0.0498162 -9.28833 40.3374 12.5794" width="40.3374pt" 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="M300 -147C201 -63 143 98 143 270S200 602 300 686L282 710C136 610 70 450 70 271V270C70 89 136 -72 282 -170L300 -147Z"></path></g><g transform="matrix(.013,0,0,-0.013,4.498,0)"><path d="M592 498C586 556 582 629 581 675H560C545 656 537 650 510 650H115C87 650 74 652 60 675H40C38 620 33 555 28 495H57C69 539 77 568 89 585C102 607 122 616 205 616H267V123C267 44 259 34 168 28V0H454V28C360 34 352 44 352 123V616H422C498 616 514 608 531 584C542 568 552 543 562 495L592 498Z"></path></g><g transform="matrix(.013,0,0,-0.013,12.31,0)"><path d="M135 536C164 536 186 560 186 587C186 617 164 639 136 639C109 639 85 617 85 587C85 560 109 536 135 536ZM252 0V26C188 32 181 38 181 106V451C138 433 90 420 39 412V388C99 379 102 374 102 312V106C102 38 95 32 32 26V0H252Z"></path></g><g transform="matrix(.013,0,0,-0.013,15.837,0)"><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,-0.0091,25.585,3.132)"><path d="M414 144C384 79 371 75 317 75H135L276 221C367 316 408 376 408 465C408 570 327 635 237 635C179 635 131 609 100 575L42 494L67 471C94 510 138 565 205 565C277 565 321 517 321 435C321 348 258 270 195 195C146 137 88 81 33 26V0H411C423 44 433 88 446 135L414 144Z"></path></g><g transform="matrix(.013,0,0,-0.013,30.531,0)"><path d="M275 270C275 450 212 609 64 710L45 686C145 604 203 442 203 270S147 -63 45 -147L64 -170C213 -68 275 89 275 270Z"></path></g><g transform="matrix(.0091,0,0,-0.0091,35.029,3.132)"><path d="M504 89L488 119C453 85 428 69 416 69C408 69 405 75 412 102L462 304C492 438 460 451 436 451S388 441 356 423C311 397 229 336 170 256H168L189 340C208 418 200 451 177 451C144 451 82 413 24 352L40 322C65 345 98 369 108 369C114 369 119 363 112 335L28 -3L36 -12C54 -3 83 4 112 10C125 73 138 122 153 174C205 258 328 382 376 382C395 382 399 369 384 305L330 93C312 25 323 -12 351 -12C378 -12 439 21 504 89Z"></path></g></svg>;</span> (c) diameter of <svg height="12.5794pt" id="M106" style="vertical-align:-3.29107pt" version="1.1" viewbox="-0.0498162 -9.28833 40.3374 12.5794" width="40.3374pt" 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="M300 -147C201 -63 143 98 143 270S200 602 300 686L282 710C136 610 70 450 70 271V270C70 89 136 -72 282 -170L300 -147Z"></path></g><g transform="matrix(.013,0,0,-0.013,4.498,0)"><path d="M592 498C586 556 582 629 581 675H560C545 656 537 650 510 650H115C87 650 74 652 60 675H40C38 620 33 555 28 495H57C69 539 77 568 89 585C102 607 122 616 205 616H267V123C267 44 259 34 168 28V0H454V28C360 34 352 44 352 123V616H422C498 616 514 608 531 584C542 568 552 543 562 495L592 498Z"></path></g><g transform="matrix(.013,0,0,-0.013,12.31,0)"><path d="M135 536C164 536 186 560 186 587C186 617 164 639 136 639C109 639 85 617 85 587C85 560 109 536 135 536ZM252 0V26C188 32 181 38 181 106V451C138 433 90 420 39 412V388C99 379 102 374 102 312V106C102 38 95 32 32 26V0H252Z"></path></g><g transform="matrix(.013,0,0,-0.013,15.837,0)"><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,-0.0091,25.585,3.132)"><path d="M414 144C384 79 371 75 317 75H135L276 221C367 316 408 376 408 465C408 570 327 635 237 635C179 635 131 609 100 575L42 494L67 471C94 510 138 565 205 565C277 565 321 517 321 435C321 348 258 270 195 195C146 137 88 81 33 26V0H411C423 44 433 88 446 135L414 144Z"></path></g><g transform="matrix(.013,0,0,-0.013,30.531,0)"><path d="M275 270C275 450 212 609 64 710L45 686C145 604 203 442 203 270S147 -63 45 -147L64 -170C213 -68 275 89 275 270Z"></path></g><g transform="matrix(.0091,0,0,-0.0091,35.029,3.132)"><path d="M504 89L488 119C453 85 428 69 416 69C408 69 405 75 412 102L462 304C492 438 460 451 436 451S388 441 356 423C311 397 229 336 170 256H168L189 340C208 418 200 451 177 451C144 451 82 413 24 352L40 322C65 345 98 369 108 369C114 369 119 363 112 335L28 -3L36 -12C54 -3 83 4 112 10C125 73 138 122 153 174C205 258 328 382 376 382C395 382 399 369 384 305L330 93C312 25 323 -12 351 -12C378 -12 439 21 504 89Z"></path></g></svg> NPs; (d) the exciton binding energy of <svg height="12.5794pt" id="M107" style="vertical-align:-3.29107pt" version="1.1" viewbox="-0.0498162 -9.28833 40.3374 12.5794" width="40.3374pt" 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="M300 -147C201 -63 143 98 143 270S200 602 300 686L282 710C136 610 70 450 70 271V270C70 89 136 -72 282 -170L300 -147Z"></path></g><g transform="matrix(.013,0,0,-0.013,4.498,0)"><path d="M592 498C586 556 582 629 581 675H560C545 656 537 650 510 650H115C87 650 74 652 60 675H40C38 620 33 555 28 495H57C69 539 77 568 89 585C102 607 122 616 205 616H267V123C267 44 259 34 168 28V0H454V28C360 34 352 44 352 123V616H422C498 616 514 608 531 584C542 568 552 543 562 495L592 498Z"></path></g><g transform="matrix(.013,0,0,-0.013,12.31,0)"><path d="M135 536C164 536 186 560 186 587C186 617 164 639 136 639C109 639 85 617 85 587C85 560 109 536 135 536ZM252 0V26C188 32 181 38 181 106V451C138 433 90 420 39 412V388C99 379 102 374 102 312V106C102 38 95 32 32 26V0H252Z"></path></g><g transform="matrix(.013,0,0,-0.013,15.837,0)"><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,-0.0091,25.585,3.132)"><path d="M414 144C384 79 371 75 317 75H135L276 221C367 316 408 376 408 465C408 570 327 635 237 635C179 635 131 609 100 575L42 494L67 471C94 510 138 565 205 565C277 565 321 517 321 435C321 348 258 270 195 195C146 137 88 81 33 26V0H411C423 44 433 88 446 135L414 144Z"></path></g><g transform="matrix(.013,0,0,-0.013,30.531,0)"><path d="M275 270C275 450 212 609 64 710L45 686C145 604 203 442 203 270S147 -63 45 -147L64 -170C213 -68 275 89 275 270Z"></path></g><g transform="matrix(.0091,0,0,-0.0091,35.029,3.132)"><path d="M504 89L488 119C453 85 428 69 416 69C408 69 405 75 412 102L462 304C492 438 460 451 436 451S388 441 356 423C311 397 229 336 170 256H168L189 340C208 418 200 451 177 451C144 451 82 413 24 352L40 322C65 345 98 369 108 369C114 369 119 363 112 335L28 -3L36 -12C54 -3 83 4 112 10C125 73 138 122 153 174C205 258 328 382 376 382C395 382 399 369 384 305L330 93C312 25 323 -12 351 -12C378 -12 439 21 504 89Z"></path></g></svg> NPs.</div>

International Journal of Photoenergy

fig6

Figure 6

Figure 6: Strongly Bound Frenkel Excitons on TiO<sub>2</sub> Nanoparticles: An Evolutionary and DFT Approach 

International Journal of Photoenergy

Strongly Bound Frenkel Excitons on TiO2 Nanoparticles: An Evolutionary and DFT Approach

Figure 6

Strongly Bound Frenkel Excitons on TiO₂ Nanoparticles: An Evolutionary and DFT Approach