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

<div>1s XAS projection of a calculated 1s2p RIXS map for <svg height="11.6412pt" id="M842" style="vertical-align:-0.04979992pt" version="1.1" viewbox="-0.0498162 -11.5914 29.2997 11.6412" width="29.2997pt" 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="M861 0V28C774 35 771 41 768 147L759 509C756 612 762 614 851 622V650H681L449 149L221 650H57V622C148 613 153 609 144 479L130 271C123 166 117 123 111 88C104 46 85 34 26 28V0H259V28C192 35 169 42 167 90C166 130 166 173 170 256L185 541H187L411 7H431L675 555H679L683 147C683 41 680 35 598 28V0H861Z" id="g121-75"></path></g><g transform="matrix(.013,0,0,-0.013,11.492,0)"><path d="M524 0V26C466 32 460 36 460 104V297C460 393 411 449 331 449C302 449 276 437 248 419C223 402 201 387 181 372V451C137 432 90 420 42 411V388C96 378 102 374 102 310V104C102 38 97 33 29 26V0H246V26C187 32 181 36 181 104V339C211 365 250 390 290 390C357 390 381 345 381 276V109C381 40 374 32 315 26V0H524Z" id="g121-108"></path></g><g transform="matrix(.0091,0,0,-0.0091,18.673,-5.741)"><path d="M290 377C321 398 342 415 358 430C378 450 389 473 389 502C389 578 329 635 238 635H237C184 635 137 610 109 578L64 515L88 493C112 529 154 573 208 573S303 542 303 482C303 409 233 370 141 341L149 308C165 313 190 319 215 319C272 319 341 283 341 193C342 98 292 43 222 43C163 43 122 72 96 94C88 101 79 100 70 94C61 87 47 73 46 60C44 47 48 37 62 23C76 10 118 -12 165 -12C238 -12 430 62 430 223C430 297 379 359 290 375V377Z" id="g50-52"></path></g><g transform="matrix(.0091,0,0,-0.0091,23.105,-5.741)"><path d="M556 236V289H337V504H275V289H56V236H275V-4H337V236H556Z" id="g54-36"></path></g></svg> (<svg height="11.8369pt" id="M843" 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="M462 177V227H365V632H320C217 496 116 350 21 208V177H284V109C284 43 280 38 190 31V0H451V31C369 38 365 43 365 108V177H462ZM284 227H88C155 336 218 430 282 519H284V227Z" id="g50-53"></path></g></svg>) with the corresponding ELD. The high spin to low spin transition at approximately <svg height="11.8174pt" id="M844" style="vertical-align:-3.42942pt" version="1.1" viewbox="-0.0498162 -8.38798 82.207 11.8174" width="82.207pt" 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="M384 0V27C293 34 287 42 287 114V635C232 613 172 594 109 583V559L157 557C201 555 205 550 205 499V114C205 42 199 34 109 27V0H384Z" id="g113-50"></path></g><g transform="matrix(.013,0,0,-0.013,6.24,0)"><path d="M241 635C89 635 35 457 35 312C35 153 89 -12 240 -12C390 -12 443 166 443 312C443 466 390 635 241 635ZM238 602C329 602 354 454 354 312C354 172 330 22 240 22C152 22 124 173 124 313S148 602 238 602Z" id="g113-49"></path></g><g transform="matrix(.013,0,0,-0.013,12.48,0)"><path d="M43 650V622C120 616 128 612 128 526V124C128 39 120 33 34 27V0H270C392 0 492 25 567 83C643 141 690 230 690 350C690 444 655 517 605 565C543 625 450 650 323 650H43ZM213 547C213 587 217 598 226 604C236 612 262 617 304 617C371 617 429 604 474 576C554 529 592 439 592 336C592 176 505 36 319 36C246 36 213 55 213 131V547Z" id="g121-66"></path></g><g transform="matrix(.013,0,0,-0.013,22.035,0)"><path d="M474 429L457 433C435 440 389 448 367 448C348 448 323 446 309 443C266 434 195 406 148 366C78 307 23 210 23 101C23 35 55 -12 92 -12C118 -12 146 1 196 35C247 70 311 130 346 173H348L281 -148C268 -211 256 -221 208 -229L191 -232L187 -257L433 -245L437 -219L411 -216C357 -210 350 -205 362 -140L427 207C447 315 461 381 474 429ZM387 387C379 337 363 262 355 236C318 180 201 57 142 57C126 57 112 81 112 128C112 205 150 321 220 376C244 395 280 403 312 403C345 403 370 396 387 387Z" id="g113-114"></path></g><g transform="matrix(.013,0,0,-0.013,32.05,0)"><path d="M537 353L508 390C487 357 455 333 417 333C389 333 344 353 309 370C265 391 212 414 172 414C122 414 79 382 50 340L81 307C101 339 134 364 172 364C198 364 245 343 280 326C324 305 375 283 417 283C466 283 507 314 537 353ZM537 168L508 205C487 172 455 148 417 148C389 148 344 168 309 185C265 206 212 229 172 229C122 229 79 197 50 155L81 122C101 154 134 179 172 179C198 179 245 158 280 141C324 120 375 98 417 98C466 98 507 129 537 168Z" id="g117-132"></path></g><g transform="matrix(.013,0,0,-0.013,43.313,0)"><path d="M412 140C382 77 369 73 315 73H129L270 222C362 320 402 379 402 466C402 571 322 635 234 635C177 635 130 609 99 576L42 495L64 475C90 514 133 568 201 568C274 568 318 519 318 435C318 349 255 267 193 193C144 135 87 78 32 23V0H405C417 45 427 89 440 131L412 140Z" id="g113-51"></path></g><g transform="matrix(.013,0,0,-0.013,49.553,0)"><path d="M113 -12C146 -12 170 11 170 46C170 78 146 103 114 103S58 78 58 46C58 11 82 -12 113 -12Z" id="g113-47"></path></g><g transform="matrix(.013,0,0,-0.013,52.517,0)"><path d="M249 635C141 635 70 555 70 471C70 401 114 353 179 316C143 294 106 267 90 252C68 231 45 202 45 157C45 50 130 -12 237 -12C322 -12 435 52 435 169C435 256 372 304 303 343C349 374 375 398 383 407C401 429 411 458 411 487C411 569 344 635 249 635ZM238 603C285 603 337 567 337 482C337 422 310 385 276 358C205 393 145 426 145 500C145 552 179 603 238 603ZM248 20C183 20 125 70 125 163C125 218 158 268 206 300C284 261 355 217 355 143C355 66 308 20 248 20Z" id="g113-57"></path></g><g transform="matrix(.013,0,0,-0.013,58.757,0)"><path d="M153 550H386L412 615L406 623H120L82 318C104 327 142 338 184 338C294 338 347 275 347 187C347 112 305 39 221 39C160 39 119 71 97 89C88 97 80 96 71 90C59 80 50 67 49 57C48 45 52 36 66 23C80 9 123 -12 169 -12C221 -11 288 15 342 59C403 109 431 165 431 225C431 308 366 395 238 395C212 395 165 379 127 364L153 550Z" id="g113-54"></path></g><g transform="matrix(.013,0,0,-0.013,67.172,0)"><path d="M380 106C343 72 306 56 265 56C195 56 116 112 115 248C235 252 361 262 377 265C396 269 400 277 400 297C400 374 333 449 250 449H249C198 449 144 421 103 376S37 269 37 201C37 88 109 -12 232 -12C263 -12 332 6 395 84L380 106ZM225 412C281 412 315 364 314 312C314 297 308 292 290 292C232 290 176 289 120 289C135 370 180 412 225 412Z" id="g121-99"></path></g><g transform="matrix(.013,0,0,-0.013,72.698,0)"><path d="M687 650H462V622C543 612 549 605 530 547C498 447 422 252 372 126H370C302 298 229 492 204 563C188 607 191 615 262 622V650H17V622C77 616 93 608 122 534C180 389 262 172 329 -11H360C436 196 541 450 568 516C606 605 619 614 687 622V650Z" id="g121-84"></path></g></svg> can be recognised. In fact, there are two HS → LS transitions: in the ground and the intermediate state.</div>

Journal of Spectroscopy

fig31

Figure 31

Figure 31: 1s2p RIXS Calculations for 3d Transition Metal Ions in Octahedral Symmetry 