{"bundle_type":"pith_open_graph_bundle","bundle_version":"1.0","pith_number":"pith:2018:YG5L4A2GQFVOAXD4ZZCZNZ3DUU","short_pith_number":"pith:YG5L4A2G","canonical_record":{"source":{"id":"1811.09945","kind":"arxiv","version":1},"metadata":{"license":"http://arxiv.org/licenses/nonexclusive-distrib/1.0/","primary_cat":"physics.chem-ph","submitted_at":"2018-11-25T05:03:29Z","cross_cats_sorted":[],"title_canon_sha256":"0f5a6870abe297d6e1177eb1aba09090e3c1f0f21b20f9dbb9c79c713249f54e","abstract_canon_sha256":"ae5e815f9f864c2f260f0004f7f775632e2052bbe44098af728ea281f63c6394"},"schema_version":"1.0"},"canonical_sha256":"c1babe0346816ae05c7cce4596e763a535bfdd82b8986db48e9a3159b103ce3b","source":{"kind":"arxiv","id":"1811.09945","version":1},"source_aliases":[{"alias_kind":"arxiv","alias_value":"1811.09945","created_at":"2026-05-17T23:50:11Z"},{"alias_kind":"arxiv_version","alias_value":"1811.09945v1","created_at":"2026-05-17T23:50:11Z"},{"alias_kind":"doi","alias_value":"10.48550/arxiv.1811.09945","created_at":"2026-05-17T23:50:11Z"},{"alias_kind":"pith_short_12","alias_value":"YG5L4A2GQFVO","created_at":"2026-05-18T12:33:04Z"},{"alias_kind":"pith_short_16","alias_value":"YG5L4A2GQFVOAXD4","created_at":"2026-05-18T12:33:04Z"},{"alias_kind":"pith_short_8","alias_value":"YG5L4A2G","created_at":"2026-05-18T12:33:04Z"}],"events":[{"event_type":"record_created","subject_pith_number":"pith:2018:YG5L4A2GQFVOAXD4ZZCZNZ3DUU","target":"record","payload":{"canonical_record":{"source":{"id":"1811.09945","kind":"arxiv","version":1},"metadata":{"license":"http://arxiv.org/licenses/nonexclusive-distrib/1.0/","primary_cat":"physics.chem-ph","submitted_at":"2018-11-25T05:03:29Z","cross_cats_sorted":[],"title_canon_sha256":"0f5a6870abe297d6e1177eb1aba09090e3c1f0f21b20f9dbb9c79c713249f54e","abstract_canon_sha256":"ae5e815f9f864c2f260f0004f7f775632e2052bbe44098af728ea281f63c6394"},"schema_version":"1.0"},"canonical_sha256":"c1babe0346816ae05c7cce4596e763a535bfdd82b8986db48e9a3159b103ce3b","receipt":{"kind":"pith_receipt","key_id":"pith-v1-2026-05","algorithm":"ed25519","signed_at":"2026-05-17T23:50:11.232693Z","signature_b64":"B+5ZE9zZ8PDSFxnvuxbIBlnuQ3dkSp5MGa9c7G8b80UiD3C00eWH0PFVt+7Oz38Ja+Evq+tBUgva3DMJd8+NAw==","signed_message":"canonical_sha256_bytes","builder_version":"pith-number-builder-2026-05-17-v1","receipt_version":"0.3","canonical_sha256":"c1babe0346816ae05c7cce4596e763a535bfdd82b8986db48e9a3159b103ce3b","last_reissued_at":"2026-05-17T23:50:11.232244Z","signature_status":"signed_v1","first_computed_at":"2026-05-17T23:50:11.232244Z","public_key_fingerprint":"8d4b5ee74e4693bcd1df2446408b0d54"},"source_kind":"arxiv","source_id":"1811.09945","source_version":1,"attestation_state":"computed"},"signer":{"signer_id":"pith.science","signer_type":"pith_registry","key_id":"pith-v1-2026-05","public_key_fingerprint":"8d4b5ee74e4693bcd1df2446408b0d54"},"created_at":"2026-05-17T23:50:11Z","supersedes":[],"prev_event":null,"signature":{"signature_status":"signed_v1","algorithm":"ed25519","key_id":"pith-v1-2026-05","public_key_fingerprint":"8d4b5ee74e4693bcd1df2446408b0d54","signature_b64":"l2YfAdlX5StWFpdKlOv25mpc+2U5P6q9i/j/CemL1UbnrnRWOfxxkCyxsNPSJ12OH9356MYb93Fz6ueh/9nUDg==","signed_message":"open_graph_event_sha256_bytes","signed_at":"2026-06-09T16:07:46.450845Z"},"content_sha256":"402f4ecfd0264c6cae9c72369af31fe1c347c22434c65189072b9774bb493e7c","schema_version":"1.0","event_id":"sha256:402f4ecfd0264c6cae9c72369af31fe1c347c22434c65189072b9774bb493e7c"},{"event_type":"graph_snapshot","subject_pith_number":"pith:2018:YG5L4A2GQFVOAXD4ZZCZNZ3DUU","target":"graph","payload":{"graph_snapshot":{"paper":{"title":"Nonequilibrium vibrational population and donor-acceptor vibrations affecting rates of radiationless transitions","license":"http://arxiv.org/licenses/nonexclusive-distrib/1.0/","headline":"","cross_cats":[],"primary_cat":"physics.chem-ph","authors_text":"Dmitry V. Matyushov","submitted_at":"2018-11-25T05:03:29Z","abstract_excerpt":"An analytical theory is developed for radiationless transitions in molecules characterized by nonequilibrium populations of their vibrational modes. Several changes to the standard transition-state framework follow from nonequilibrium conditions: (i) non-Arrhenius kinetics, (ii) the violation of the fluctuation-dissipation theorem (FDT), and (iii) the breakdown of the detailed balance. The violation of the FDT is reflected in the breakdown of relations between the first (Stokes shift) and second (inhomogeneous band-width) spectral moments, and of similar relations between reorganization parame"},"claims":{"count":0,"items":[],"snapshot_sha256":"258153158e38e3291e3d48162225fcdb2d5a3ed65a07baac614ab91432fd4f57"},"source":{"id":"1811.09945","kind":"arxiv","version":1},"verdict":{"id":null,"model_set":{},"created_at":null,"strongest_claim":"","one_line_summary":"","pipeline_version":null,"weakest_assumption":"","pith_extraction_headline":""},"references":{"count":0,"sample":[],"resolved_work":0,"snapshot_sha256":"258153158e38e3291e3d48162225fcdb2d5a3ed65a07baac614ab91432fd4f57","internal_anchors":0},"formal_canon":{"evidence_count":0,"snapshot_sha256":"258153158e38e3291e3d48162225fcdb2d5a3ed65a07baac614ab91432fd4f57"},"author_claims":{"count":0,"strong_count":0,"snapshot_sha256":"258153158e38e3291e3d48162225fcdb2d5a3ed65a07baac614ab91432fd4f57"},"builder_version":"pith-number-builder-2026-05-17-v1"},"verdict_id":null},"signer":{"signer_id":"pith.science","signer_type":"pith_registry","key_id":"pith-v1-2026-05","public_key_fingerprint":"8d4b5ee74e4693bcd1df2446408b0d54"},"created_at":"2026-05-17T23:50:11Z","supersedes":[],"prev_event":null,"signature":{"signature_status":"signed_v1","algorithm":"ed25519","key_id":"pith-v1-2026-05","public_key_fingerprint":"8d4b5ee74e4693bcd1df2446408b0d54","signature_b64":"gRtUT+GqFF5Pg8dH4REc03v/axwhE6zkHEv4s2whrku3pG3zaQEjBURGiaAsKx7vumkHsvjFZLWJFU2zQ2k8AA==","signed_message":"open_graph_event_sha256_bytes","signed_at":"2026-06-09T16:07:46.451189Z"},"content_sha256":"b264cec5289f0a30b0be83237408d866347a7cd34a983a6296cdf61d2eb3cdde","schema_version":"1.0","event_id":"sha256:b264cec5289f0a30b0be83237408d866347a7cd34a983a6296cdf61d2eb3cdde"}],"timestamp_proofs":[],"mirror_hints":[{"mirror_type":"https","name":"Pith Resolver","base_url":"https://pith.science","bundle_url":"https://pith.science/pith/YG5L4A2GQFVOAXD4ZZCZNZ3DUU/bundle.json","state_url":"https://pith.science/pith/YG5L4A2GQFVOAXD4ZZCZNZ3DUU/state.json","well_known_bundle_url":"https://pith.science/.well-known/pith/YG5L4A2GQFVOAXD4ZZCZNZ3DUU/bundle.json","status":"primary"}],"public_keys":[{"key_id":"pith-v1-2026-05","algorithm":"ed25519","format":"raw","public_key_b64":"stVStoiQhXFxp4s2pdzPNoqVNBMojDU/fJ2db5S3CbM=","public_key_hex":"b2d552b68890857171a78b36a5dccf368a953413288c353f7c9d9d6f94b709b3","fingerprint_sha256_b32_first128bits":"RVFV5Z2OI2J3ZUO7ERDEBCYNKS","fingerprint_sha256_hex":"8d4b5ee74e4693bcd1df2446408b0d54","rotates_at":null,"url":"https://pith.science/pith-signing-key.json","notes":"Pith uses this Ed25519 key to sign canonical record SHA-256 digests. Verify with: ed25519_verify(public_key, message=canonical_sha256_bytes, signature=base64decode(signature_b64))."}],"merge_version":"pith-open-graph-merge-v1","built_at":"2026-06-09T16:07:46Z","links":{"resolver":"https://pith.science/pith/YG5L4A2GQFVOAXD4ZZCZNZ3DUU","bundle":"https://pith.science/pith/YG5L4A2GQFVOAXD4ZZCZNZ3DUU/bundle.json","state":"https://pith.science/pith/YG5L4A2GQFVOAXD4ZZCZNZ3DUU/state.json","well_known_bundle":"https://pith.science/.well-known/pith/YG5L4A2GQFVOAXD4ZZCZNZ3DUU/bundle.json"},"state":{"state_type":"pith_open_graph_state","state_version":"1.0","pith_number":"pith:2018:YG5L4A2GQFVOAXD4ZZCZNZ3DUU","merge_version":"pith-open-graph-merge-v1","event_count":2,"valid_event_count":2,"invalid_event_count":0,"equivocation_count":0,"current":{"canonical_record":{"metadata":{"abstract_canon_sha256":"ae5e815f9f864c2f260f0004f7f775632e2052bbe44098af728ea281f63c6394","cross_cats_sorted":[],"license":"http://arxiv.org/licenses/nonexclusive-distrib/1.0/","primary_cat":"physics.chem-ph","submitted_at":"2018-11-25T05:03:29Z","title_canon_sha256":"0f5a6870abe297d6e1177eb1aba09090e3c1f0f21b20f9dbb9c79c713249f54e"},"schema_version":"1.0","source":{"id":"1811.09945","kind":"arxiv","version":1}},"source_aliases":[{"alias_kind":"arxiv","alias_value":"1811.09945","created_at":"2026-05-17T23:50:11Z"},{"alias_kind":"arxiv_version","alias_value":"1811.09945v1","created_at":"2026-05-17T23:50:11Z"},{"alias_kind":"doi","alias_value":"10.48550/arxiv.1811.09945","created_at":"2026-05-17T23:50:11Z"},{"alias_kind":"pith_short_12","alias_value":"YG5L4A2GQFVO","created_at":"2026-05-18T12:33:04Z"},{"alias_kind":"pith_short_16","alias_value":"YG5L4A2GQFVOAXD4","created_at":"2026-05-18T12:33:04Z"},{"alias_kind":"pith_short_8","alias_value":"YG5L4A2G","created_at":"2026-05-18T12:33:04Z"}],"graph_snapshots":[{"event_id":"sha256:b264cec5289f0a30b0be83237408d866347a7cd34a983a6296cdf61d2eb3cdde","target":"graph","created_at":"2026-05-17T23:50:11Z","signer":{"key_id":"pith-v1-2026-05","public_key_fingerprint":"8d4b5ee74e4693bcd1df2446408b0d54","signer_id":"pith.science","signer_type":"pith_registry"},"payload":{"graph_snapshot":{"author_claims":{"count":0,"snapshot_sha256":"258153158e38e3291e3d48162225fcdb2d5a3ed65a07baac614ab91432fd4f57","strong_count":0},"builder_version":"pith-number-builder-2026-05-17-v1","claims":{"count":0,"items":[],"snapshot_sha256":"258153158e38e3291e3d48162225fcdb2d5a3ed65a07baac614ab91432fd4f57"},"formal_canon":{"evidence_count":0,"snapshot_sha256":"258153158e38e3291e3d48162225fcdb2d5a3ed65a07baac614ab91432fd4f57"},"paper":{"abstract_excerpt":"An analytical theory is developed for radiationless transitions in molecules characterized by nonequilibrium populations of their vibrational modes. Several changes to the standard transition-state framework follow from nonequilibrium conditions: (i) non-Arrhenius kinetics, (ii) the violation of the fluctuation-dissipation theorem (FDT), and (iii) the breakdown of the detailed balance. The violation of the FDT is reflected in the breakdown of relations between the first (Stokes shift) and second (inhomogeneous band-width) spectral moments, and of similar relations between reorganization parame","authors_text":"Dmitry V. Matyushov","cross_cats":[],"headline":"","license":"http://arxiv.org/licenses/nonexclusive-distrib/1.0/","primary_cat":"physics.chem-ph","submitted_at":"2018-11-25T05:03:29Z","title":"Nonequilibrium vibrational population and donor-acceptor vibrations affecting rates of radiationless transitions"},"references":{"count":0,"internal_anchors":0,"resolved_work":0,"sample":[],"snapshot_sha256":"258153158e38e3291e3d48162225fcdb2d5a3ed65a07baac614ab91432fd4f57"},"source":{"id":"1811.09945","kind":"arxiv","version":1},"verdict":{"created_at":null,"id":null,"model_set":{},"one_line_summary":"","pipeline_version":null,"pith_extraction_headline":"","strongest_claim":"","weakest_assumption":""}},"verdict_id":null}}],"author_attestations":[],"timestamp_anchors":[],"storage_attestations":[],"citation_signatures":[],"replication_records":[],"corrections":[],"mirror_hints":[],"record_created":{"event_id":"sha256:402f4ecfd0264c6cae9c72369af31fe1c347c22434c65189072b9774bb493e7c","target":"record","created_at":"2026-05-17T23:50:11Z","signer":{"key_id":"pith-v1-2026-05","public_key_fingerprint":"8d4b5ee74e4693bcd1df2446408b0d54","signer_id":"pith.science","signer_type":"pith_registry"},"payload":{"attestation_state":"computed","canonical_record":{"metadata":{"abstract_canon_sha256":"ae5e815f9f864c2f260f0004f7f775632e2052bbe44098af728ea281f63c6394","cross_cats_sorted":[],"license":"http://arxiv.org/licenses/nonexclusive-distrib/1.0/","primary_cat":"physics.chem-ph","submitted_at":"2018-11-25T05:03:29Z","title_canon_sha256":"0f5a6870abe297d6e1177eb1aba09090e3c1f0f21b20f9dbb9c79c713249f54e"},"schema_version":"1.0","source":{"id":"1811.09945","kind":"arxiv","version":1}},"canonical_sha256":"c1babe0346816ae05c7cce4596e763a535bfdd82b8986db48e9a3159b103ce3b","receipt":{"algorithm":"ed25519","builder_version":"pith-number-builder-2026-05-17-v1","canonical_sha256":"c1babe0346816ae05c7cce4596e763a535bfdd82b8986db48e9a3159b103ce3b","first_computed_at":"2026-05-17T23:50:11.232244Z","key_id":"pith-v1-2026-05","kind":"pith_receipt","last_reissued_at":"2026-05-17T23:50:11.232244Z","public_key_fingerprint":"8d4b5ee74e4693bcd1df2446408b0d54","receipt_version":"0.3","signature_b64":"B+5ZE9zZ8PDSFxnvuxbIBlnuQ3dkSp5MGa9c7G8b80UiD3C00eWH0PFVt+7Oz38Ja+Evq+tBUgva3DMJd8+NAw==","signature_status":"signed_v1","signed_at":"2026-05-17T23:50:11.232693Z","signed_message":"canonical_sha256_bytes"},"source_id":"1811.09945","source_kind":"arxiv","source_version":1}}},"equivocations":[],"invalid_events":[],"applied_event_ids":["sha256:402f4ecfd0264c6cae9c72369af31fe1c347c22434c65189072b9774bb493e7c","sha256:b264cec5289f0a30b0be83237408d866347a7cd34a983a6296cdf61d2eb3cdde"],"state_sha256":"b0feda9658abc12cadab919e229b7133a7116f156c430fba135c592b2a909a09"},"bundle_signature":{"signature_status":"signed_v1","algorithm":"ed25519","key_id":"pith-v1-2026-05","public_key_fingerprint":"8d4b5ee74e4693bcd1df2446408b0d54","signature_b64":"tktw6PwyeE8wJRBBh4RVN+ePXpsB5PSSGGvAU4WOMZYYYtf2V3d0M1ABtwipSCJrcyPRevCNkWjFh+UyjwzwAQ==","signed_message":"bundle_sha256_bytes","signed_at":"2026-06-09T16:07:46.454142Z","bundle_sha256":"589d0b34e47355b0ee0ebc31543523accc5a30c3339953dc445ffc761efffee0"}}