1s2p RIXS Calculations for 3d Transition Metal Ions in Octahedral Symmetry

<div>Multielectronic term scheme for <svg height="11.7587pt" id="M540" style="vertical-align:-0.1673002pt" version="1.1" viewbox="-0.0498162 -11.5914 23.5453 11.7587" width="23.5453pt" 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="M719 650H483V622C553 619 576 606 581 560C585 532 588 487 588 394V148H585L167 650H20V622C67 618 88 610 109 585C127 562 129 557 129 484V264C129 173 126 124 123 93C118 44 92 31 35 28V0H272V28C204 32 181 44 176 95C173 124 170 172 170 264V515H172L598 -9H629V394C629 487 631 532 635 563C639 606 663 619 719 622V650Z" id="g121-76"></path></g><g transform="matrix(.013,0,0,-0.013,9.385,0)"><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" id="g121-103"></path></g><g transform="matrix(.0091,0,0,-0.0091,12.918,-5.741)"><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" id="g50-51"></path></g><g transform="matrix(.0091,0,0,-0.0091,17.35,-5.741)"><path d="M556 236V289H337V504H275V289H56V236H275V-4H337V236H556Z" id="g54-36"></path></g></svg> <svg height="13.8595pt" id="M541" style="vertical-align:-2.2681pt" version="1.1" viewbox="-0.0498162 -11.5914 27.2289 13.8595" width="27.2289pt" 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" id="g113-41"></path></g><g transform="matrix(.013,0,0,-0.013,4.498,0)"><path d="M285 378C315 398 338 416 353 432C373 451 384 474 384 503C384 579 325 635 236 635H235C182 635 136 610 108 579L65 516L85 496C110 533 150 575 205 575C258 575 300 543 300 481C300 407 232 369 141 339L147 310C163 315 188 321 211 321C268 321 338 284 338 192C338 94 288 40 217 40C160 40 119 68 93 91C85 98 77 97 69 91C60 84 47 71 46 58C44 46 48 35 62 22C75 10 116 -12 162 -12C234 -12 424 62 424 224C424 297 373 359 285 376V378Z" id="g113-52"></path></g><g transform="matrix(.013,0,0,-0.013,10.738,0)"><path d="M517 51L485 54C448 58 441 63 441 115V712C404 700 337 684 285 678V653C357 648 362 645 362 580V437C339 446 309 449 295 449C159 449 38 340 38 201C38 61 143 -12 223 -12C234 -12 261 -6 301 17L362 53V-12C420 9 495 22 517 26V51ZM362 85C338 67 301 51 266 51C201 51 128 109 128 228C128 373 212 411 259 411C296 411 338 395 362 360V85Z" id="g121-98"></path></g><g transform="matrix(.0091,0,0,-0.0091,17.602,-5.741)"><path d="M253 635C142 635 71 555 71 471C71 401 113 353 178 316C144 294 106 267 91 252C70 231 46 202 46 157C46 51 132 -12 241 -12C328 -12 442 52 442 168C442 257 379 305 311 343C354 373 380 398 388 407C406 428 417 458 417 487C417 568 348 635 253 635ZM240 600C288 600 340 563 340 481C340 423 313 387 279 360C207 394 148 427 148 499C148 549 182 600 240 600ZM252 23C188 23 129 73 129 163C129 217 162 266 211 298C289 260 360 217 360 144C360 69 312 23 252 23Z" id="g50-57"></path></g><g transform="matrix(.013,0,0,-0.013,22.549,0)"><path d="M275 270C275 450 212 609 64 710L45 686C145 604 203 442 203 270S147 -63 45 -147L64 -170C213 -68 275 89 275 270Z" id="g113-42"></path></g></svg> comparing the 1s2p RIXS and direct 2p XAS pathways. Populating the <svg height="14.2954pt" id="M542" style="vertical-align:-5.528999pt" version="1.1" viewbox="-0.0498162 -8.7664 18.3766 14.2954" width="18.3766pt" 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="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" id="g121-82"></path></g><g transform="matrix(.0091,0,0,-0.0091,8.021,3.132)"><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" id="g50-51"></path></g><g transform="matrix(.0091,0,0,-0.0091,12.453,3.132)"><path d="M554 433L549 437C539 437 513 441 503 443C481 447 456 451 436 451C354 451 268 415 216 368C150 308 99 205 99 106C99 24 136 -12 165 -12C196 -12 243 14 268 33C318 70 374 118 415 181H419L395 39C374 -84 332 -149 295 -175C269 -193 245 -197 212 -197C137 -197 93 -156 76 -102C71 -87 61 -87 51 -96C36 -110 24 -130 24 -147C24 -183 76 -257 171 -257C226 -257 285 -227 323 -200C387 -155 455 -76 480 94C499 225 538 391 554 433ZM460 386C457 361 438 287 426 254C408 218 373 176 332 133C294 93 246 61 217 61C198 61 186 80 186 122C186 167 206 250 231 294C262 349 288 375 317 387C334 394 358 400 381 400C413 400 439 393 460 386Z" id="g50-104"></path></g></svg> intermediate state would require a two-electron transition in <span class="nowrap"><svg height="11.8369pt" id="M543" style="vertical-align:-0.2454996pt" version="1.1" viewbox="-0.0498162 -11.5914 18.1992 11.8369" width="18.1992pt" 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="M285 378C315 398 338 416 353 432C373 451 384 474 384 503C384 579 325 635 236 635H235C182 635 136 610 108 579L65 516L85 496C110 533 150 575 205 575C258 575 300 543 300 481C300 407 232 369 141 339L147 310C163 315 188 321 211 321C268 321 338 284 338 192C338 94 288 40 217 40C160 40 119 68 93 91C85 98 77 97 69 91C60 84 47 71 46 58C44 46 48 35 62 22C75 10 116 -12 162 -12C234 -12 424 62 424 224C424 297 373 359 285 376V378Z" id="g113-52"></path></g><g transform="matrix(.013,0,0,-0.013,6.24,0)"><path d="M517 51L485 54C448 58 441 63 441 115V712C404 700 337 684 285 678V653C357 648 362 645 362 580V437C339 446 309 449 295 449C159 449 38 340 38 201C38 61 143 -12 223 -12C234 -12 261 -6 301 17L362 53V-12C420 9 495 22 517 26V51ZM362 85C338 67 301 51 266 51C201 51 128 109 128 228C128 373 212 411 259 411C296 411 338 395 362 360V85Z" id="g121-98"></path></g><g transform="matrix(.0091,0,0,-0.0091,13.104,-5.741)"><path d="M253 635C142 635 71 555 71 471C71 401 113 353 178 316C144 294 106 267 91 252C70 231 46 202 46 157C46 51 132 -12 241 -12C328 -12 442 52 442 168C442 257 379 305 311 343C354 373 380 398 388 407C406 428 417 458 417 487C417 568 348 635 253 635ZM240 600C288 600 340 563 340 481C340 423 313 387 279 360C207 394 148 427 148 499C148 549 182 600 240 600ZM252 23C188 23 129 73 129 163C129 217 162 266 211 298C289 260 360 217 360 144C360 69 312 23 252 23Z" id="g50-57"></path></g></svg>.</span></div>

Journal of Spectroscopy

fig19

Figure 19

Figure 19: 1s2p RIXS Calculations for 3d Transition Metal Ions in Octahedral Symmetry 